[{"user_id":"68b8ca59-c5b3-11ee-8790-cd641c68093d","publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"author":[{"last_name":"Wang","first_name":"Xiye","full_name":"Wang, Xiye"},{"last_name":"Zhang","first_name":"Boyuan","full_name":"Zhang, Boyuan"},{"full_name":"Fowler, Brandon","last_name":"Fowler","first_name":"Brandon"},{"last_name":"Venkataraman","first_name":"Latha","full_name":"Venkataraman, Latha","orcid":"0000-0002-6957-6089","id":"9ebb78a5-cc0d-11ee-8322-fae086a32caf"},{"full_name":"Rovis, Tomislav","first_name":"Tomislav","last_name":"Rovis"}],"day":"25","date_published":"2023-05-25T00:00:00Z","article_processing_charge":"No","publisher":"American Chemical Society","citation":{"mla":"Wang, Xiye, et al. “Alkane Solvent-Derived Acylation Reaction Driven by Electric Fields.” <i>Journal of the American Chemical Society</i>, vol. 145, no. 22, American Chemical Society, 2023, pp. 11903–06, doi:<a href=\"https://doi.org/10.1021/jacs.3c02064\">10.1021/jacs.3c02064</a>.","apa":"Wang, X., Zhang, B., Fowler, B., Venkataraman, L., &#38; Rovis, T. (2023). Alkane solvent-derived acylation reaction driven by electric fields. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.3c02064\">https://doi.org/10.1021/jacs.3c02064</a>","short":"X. Wang, B. Zhang, B. Fowler, L. Venkataraman, T. Rovis, Journal of the American Chemical Society 145 (2023) 11903–11906.","ama":"Wang X, Zhang B, Fowler B, Venkataraman L, Rovis T. Alkane solvent-derived acylation reaction driven by electric fields. <i>Journal of the American Chemical Society</i>. 2023;145(22):11903-11906. doi:<a href=\"https://doi.org/10.1021/jacs.3c02064\">10.1021/jacs.3c02064</a>","chicago":"Wang, Xiye, Boyuan Zhang, Brandon Fowler, Latha Venkataraman, and Tomislav Rovis. “Alkane Solvent-Derived Acylation Reaction Driven by Electric Fields.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2023. <a href=\"https://doi.org/10.1021/jacs.3c02064\">https://doi.org/10.1021/jacs.3c02064</a>.","ieee":"X. Wang, B. Zhang, B. Fowler, L. Venkataraman, and T. Rovis, “Alkane solvent-derived acylation reaction driven by electric fields,” <i>Journal of the American Chemical Society</i>, vol. 145, no. 22. American Chemical Society, pp. 11903–11906, 2023.","ista":"Wang X, Zhang B, Fowler B, Venkataraman L, Rovis T. 2023. Alkane solvent-derived acylation reaction driven by electric fields. Journal of the American Chemical Society. 145(22), 11903–11906."},"issue":"22","intvolume":"       145","doi":"10.1021/jacs.3c02064","volume":145,"type":"journal_article","external_id":{"pmid":["37227235"]},"quality_controlled":"1","month":"05","article_type":"original","publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"date_updated":"2024-11-25T12:29:49Z","scopus_import":"1","oa_version":"None","publication_status":"published","page":"11903-11906","pmid":1,"year":"2023","abstract":[{"lang":"eng","text":"Electric field acceleration of alkyl hydroperoxide activation to acylate amines in the scanning tunneling microscope-based break-junction is reported. Alkyl hydroperoxide mixtures, generated from hydrocarbon autoxidation in air, were found to be competent reagents for the functionalization of gold surfaces. Intermolecular coupling on the surface in the presence of amines was observed, yielding normal alkylamides. This novel mode of alkyl hydroperoxide activation to generate acylium equivalents was found to be responsive to the magnitude of the bias in the break junction, indicating an electric field influence on this novel reactivity."}],"date_created":"2024-09-06T12:55:12Z","extern":"1","title":"Alkane solvent-derived acylation reaction driven by electric fields","_id":"17862","status":"public"},{"date_updated":"2024-11-25T14:21:10Z","oa_version":"None","scopus_import":"1","OA_type":"closed access","publication_status":"published","page":"2492-2498","pmid":1,"year":"2023","date_created":"2024-09-06T12:57:45Z","abstract":[{"text":"Molecular one-dimensional topological insulators (1D TIs), which conduct through energetically low-lying topological edge states, can be extremely highly conducting and exhibit a reversed conductance decay, affording them great potential as building blocks for nanoelectronic devices. However, these properties can only be observed at the short length limit. To extend the length at which these anomalous effects can be observed, we design topological oligo[n]emeraldine wires using short 1D TIs as building blocks. As the wire length increases, the number of topological states increases, enabling an increased electronic transmission along the wire; specifically, we show that we can drive over a microampere current through a single ∼5 nm molecular wire, appreciably more than what has been observed in other long wires reported to date. Calculations and experiments show that the longest oligo[7]emeraldine with doped topological states has over 106 enhancements in the transmission compared to its pristine form. The discovery of these highly conductive, long organic wires helps overcome a fundamental hurdle to implementing molecules in complex, nanoscale circuitry: their structures become too insulating at lengths that are useful in designing nanoscale circuits.","lang":"eng"}],"extern":"1","title":"Topological radical pairs produce ultrahigh conductance in long molecular wires","status":"public","_id":"17864","language":[{"iso":"eng"}],"user_id":"68b8ca59-c5b3-11ee-8790-cd641c68093d","publication":"Journal of the American Chemical Society","author":[{"last_name":"Li","first_name":"Liang","full_name":"Li, Liang"},{"full_name":"Louie, Shayan","first_name":"Shayan","last_name":"Louie"},{"first_name":"Austin M.","last_name":"Evans","full_name":"Evans, Austin M."},{"last_name":"Meirzadeh","first_name":"Elena","full_name":"Meirzadeh, Elena"},{"last_name":"Nuckolls","first_name":"Colin","full_name":"Nuckolls, Colin"},{"orcid":"0000-0002-6957-6089","id":"9ebb78a5-cc0d-11ee-8322-fae086a32caf","last_name":"Venkataraman","first_name":"Latha","full_name":"Venkataraman, Latha"}],"article_processing_charge":"No","date_published":"2023-01-23T00:00:00Z","day":"23","citation":{"mla":"Li, Liang, et al. “Topological Radical Pairs Produce Ultrahigh Conductance in Long Molecular Wires.” <i>Journal of the American Chemical Society</i>, vol. 145, no. 4, American Chemical Society, 2023, pp. 2492–98, doi:<a href=\"https://doi.org/10.1021/jacs.2c12059\">10.1021/jacs.2c12059</a>.","apa":"Li, L., Louie, S., Evans, A. M., Meirzadeh, E., Nuckolls, C., &#38; Venkataraman, L. (2023). Topological radical pairs produce ultrahigh conductance in long molecular wires. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.2c12059\">https://doi.org/10.1021/jacs.2c12059</a>","ama":"Li L, Louie S, Evans AM, Meirzadeh E, Nuckolls C, Venkataraman L. Topological radical pairs produce ultrahigh conductance in long molecular wires. <i>Journal of the American Chemical Society</i>. 2023;145(4):2492-2498. doi:<a href=\"https://doi.org/10.1021/jacs.2c12059\">10.1021/jacs.2c12059</a>","chicago":"Li, Liang, Shayan Louie, Austin M. Evans, Elena Meirzadeh, Colin Nuckolls, and Latha Venkataraman. “Topological Radical Pairs Produce Ultrahigh Conductance in Long Molecular Wires.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2023. <a href=\"https://doi.org/10.1021/jacs.2c12059\">https://doi.org/10.1021/jacs.2c12059</a>.","ista":"Li L, Louie S, Evans AM, Meirzadeh E, Nuckolls C, Venkataraman L. 2023. Topological radical pairs produce ultrahigh conductance in long molecular wires. Journal of the American Chemical Society. 145(4), 2492–2498.","ieee":"L. Li, S. Louie, A. M. Evans, E. Meirzadeh, C. Nuckolls, and L. Venkataraman, “Topological radical pairs produce ultrahigh conductance in long molecular wires,” <i>Journal of the American Chemical Society</i>, vol. 145, no. 4. American Chemical Society, pp. 2492–2498, 2023.","short":"L. Li, S. Louie, A.M. Evans, E. Meirzadeh, C. Nuckolls, L. Venkataraman, Journal of the American Chemical Society 145 (2023) 2492–2498."},"publisher":"American Chemical Society","intvolume":"       145","issue":"4","volume":145,"doi":"10.1021/jacs.2c12059","external_id":{"pmid":["36689781"]},"type":"journal_article","month":"01","quality_controlled":"1","publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]}},{"das_tickbox":"0","isi":1,"corr_author":"1","status":"public","_id":"13216","title":"Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane","oa":1,"date_created":"2023-07-12T09:16:40Z","abstract":[{"lang":"eng","text":"Physical catalysts often have multiple sites where reactions can take place. One prominent example is single-atom alloys, where the reactive dopant atoms can preferentially locate in the bulk or at different sites on the surface of the nanoparticle. However, ab initio modeling of catalysts usually only considers one site of the catalyst, neglecting the effects of multiple sites. Here, nanoparticles of copper doped with single-atom rhodium or palladium are modeled for the dehydrogenation of propane. Single-atom alloy nanoparticles are simulated at 400–600 K, using machine learning potentials trained on density functional theory calculations, and then the occupation of different single-atom active sites is identified using a similarity kernel. Further, the turnover frequency for all possible sites is calculated for propane dehydrogenation to propene through microkinetic modeling using density functional theory calculations. The total turnover frequencies of the whole nanoparticle are then described from both the population and the individual turnover frequency of each site. Under operating conditions, rhodium as a dopant is found to almost exclusively occupy (111) surface sites while palladium as a dopant occupies a greater variety of facets. Undercoordinated dopant surface sites are found to tend to be more reactive for propane dehydrogenation compared to the (111) surface. It is found that considering the dynamics of the single-atom alloy nanoparticle has a profound effect on the calculated catalytic activity of single-atom alloys by several orders of magnitude."}],"scopus_import":"1","oa_version":"Published Version","date_updated":"2026-08-07T11:37:26Z","year":"2023","pmid":1,"page":"14894-14902","publication_status":"published","external_id":{"pmid":["37390457"],"isi":["001020623900001"]},"type":"journal_article","has_accepted_license":"1","volume":145,"doi":"10.1021/jacs.3c04030","publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"article_type":"original","month":"06","quality_controlled":"1","department":[{"_id":"MaIb"},{"_id":"BiCh"}],"acknowledgement":"B.C. acknowledges resources provided by the Cambridge Tier2 system operated by the University of Cambridge Research\r\nComputing Service funded by EPSRC Tier-2 capital grant EP/\r\nP020259/1.","author":[{"full_name":"Bunting, Rhys","first_name":"Rhys","last_name":"Bunting","id":"91deeae8-1207-11ec-b130-c194ad5b50c6","orcid":"0000-0001-6928-074X"},{"orcid":"0009-0000-1457-795X","id":"8b4b6a9f-32b0-11ee-9fa8-bbe85e26258e","first_name":"Felix","last_name":"Wodaczek","full_name":"Wodaczek, Felix"},{"first_name":"Tina","last_name":"Torabi","full_name":"Torabi, Tina"},{"full_name":"Cheng, Bingqing","first_name":"Bingqing","last_name":"Cheng","id":"cbe3cda4-d82c-11eb-8dc7-8ff94289fcc9","orcid":"0000-0002-3584-9632"}],"keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"tmp":{"name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","image":"/images/cc_by.png","short":"CC BY (4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode"},"publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"ddc":["540"],"user_id":"317138e5-6ab7-11ef-aa6d-ffef3953e345","intvolume":"       145","supplementarymaterial":"yes","issue":"27","citation":{"ama":"Bunting R, Wodaczek F, Torabi T, Cheng B. Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane. <i>Journal of the American Chemical Society</i>. 2023;145(27):14894-14902. doi:<a href=\"https://doi.org/10.1021/jacs.3c04030\">10.1021/jacs.3c04030</a>","ista":"Bunting R, Wodaczek F, Torabi T, Cheng B. 2023. Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane. Journal of the American Chemical Society. 145(27), 14894–14902.","ieee":"R. Bunting, F. Wodaczek, T. Torabi, and B. Cheng, “Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane,” <i>Journal of the American Chemical Society</i>, vol. 145, no. 27. American Chemical Society, pp. 14894–14902, 2023.","chicago":"Bunting, Rhys, Felix Wodaczek, Tina Torabi, and Bingqing Cheng. “Reactivity of Single-Atom Alloy Nanoparticles: Modeling the Dehydrogenation of Propane.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2023. <a href=\"https://doi.org/10.1021/jacs.3c04030\">https://doi.org/10.1021/jacs.3c04030</a>.","short":"R. Bunting, F. Wodaczek, T. Torabi, B. Cheng, Journal of the American Chemical Society 145 (2023) 14894–14902.","mla":"Bunting, Rhys, et al. “Reactivity of Single-Atom Alloy Nanoparticles: Modeling the Dehydrogenation of Propane.” <i>Journal of the American Chemical Society</i>, vol. 145, no. 27, American Chemical Society, 2023, pp. 14894–902, doi:<a href=\"https://doi.org/10.1021/jacs.3c04030\">10.1021/jacs.3c04030</a>.","apa":"Bunting, R., Wodaczek, F., Torabi, T., &#38; Cheng, B. (2023). Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.3c04030\">https://doi.org/10.1021/jacs.3c04030</a>"},"publisher":"American Chemical Society","researchdata_availability":"no","file":[{"file_size":3155843,"access_level":"open_access","success":1,"date_updated":"2023-07-12T10:22:04Z","content_type":"application/pdf","relation":"main_file","checksum":"e07d5323f9c0e5cbd1ad6453f29440ab","date_created":"2023-07-12T10:22:04Z","creator":"cchlebak","file_name":"2023_JACS_Bunting.pdf","file_id":"13219"}],"article_processing_charge":"Yes (via OA deal)","day":"30","date_published":"2023-06-30T00:00:00Z","file_date_updated":"2023-07-12T10:22:04Z"},{"article_processing_charge":"No","date_published":"2022-11-15T00:00:00Z","main_file_link":[{"open_access":"1","url":"https://doi.org/10.1021/jacs.2c08901"}],"day":"15","citation":{"mla":"Wang, Jinhua, et al. “Altering the Properties of Spiropyran Switches Using Coordination Cages with Different Symmetries.” <i>Journal of the American Chemical Society</i>, vol. 144, no. 46, American Chemical Society, 2022, pp. 21244–54, doi:<a href=\"https://doi.org/10.1021/jacs.2c08901\">10.1021/jacs.2c08901</a>.","apa":"Wang, J., Avram, L., Diskin-Posner, Y., Białek, M. J., Stawski, W., Feller, M., &#38; Klajn, R. (2022). Altering the properties of spiropyran switches using coordination cages with different symmetries. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.2c08901\">https://doi.org/10.1021/jacs.2c08901</a>","short":"J. Wang, L. Avram, Y. Diskin-Posner, M.J. Białek, W. Stawski, M. Feller, R. Klajn, Journal of the American Chemical Society 144 (2022) 21244–21254.","ama":"Wang J, Avram L, Diskin-Posner Y, et al. Altering the properties of spiropyran switches using coordination cages with different symmetries. <i>Journal of the American Chemical Society</i>. 2022;144(46):21244-21254. doi:<a href=\"https://doi.org/10.1021/jacs.2c08901\">10.1021/jacs.2c08901</a>","ieee":"J. Wang <i>et al.</i>, “Altering the properties of spiropyran switches using coordination cages with different symmetries,” <i>Journal of the American Chemical Society</i>, vol. 144, no. 46. American Chemical Society, pp. 21244–21254, 2022.","ista":"Wang J, Avram L, Diskin-Posner Y, Białek MJ, Stawski W, Feller M, Klajn R. 2022. Altering the properties of spiropyran switches using coordination cages with different symmetries. Journal of the American Chemical Society. 144(46), 21244–21254.","chicago":"Wang, Jinhua, Liat Avram, Yael Diskin-Posner, Michał J. Białek, Wojciech Stawski, Moran Feller, and Rafal Klajn. “Altering the Properties of Spiropyran Switches Using Coordination Cages with Different Symmetries.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2022. <a href=\"https://doi.org/10.1021/jacs.2c08901\">https://doi.org/10.1021/jacs.2c08901</a>."},"publisher":"American Chemical Society","intvolume":"       144","issue":"46","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"author":[{"first_name":"Jinhua","last_name":"Wang","full_name":"Wang, Jinhua"},{"last_name":"Avram","first_name":"Liat","full_name":"Avram, Liat"},{"first_name":"Yael","last_name":"Diskin-Posner","full_name":"Diskin-Posner, Yael"},{"first_name":"Michał J.","last_name":"Białek","full_name":"Białek, Michał J."},{"full_name":"Stawski, Wojciech","first_name":"Wojciech","last_name":"Stawski"},{"full_name":"Feller, Moran","last_name":"Feller","first_name":"Moran"},{"full_name":"Klajn, Rafal","first_name":"Rafal","last_name":"Klajn","id":"8e84690e-1e48-11ed-a02b-a1e6fb8bb53b"}],"month":"11","quality_controlled":"1","article_type":"original","publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"volume":144,"doi":"10.1021/jacs.2c08901","type":"journal_article","page":"21244-21254","publication_status":"published","year":"2022","date_updated":"2024-10-14T12:08:54Z","oa_version":"Published Version","scopus_import":"1","date_created":"2023-08-01T09:31:01Z","oa":1,"abstract":[{"lang":"eng","text":"Molecular confinement effects can profoundly alter the physicochemical properties of the confined species. A plethora of organic molecules were encapsulated within the cavities of supramolecular hosts, and the impact of the cavity size and polarity was widely investigated. However, the extent to which the properties of the confined guests can be affected by the symmetry of the cage─which dictates the shape of the cavity─remains to be understood. Here we show that cage symmetry has a dramatic effect on the equilibrium between two isomers of the encapsulated spiropyran guests. Working with two Pd-based coordination cages featuring similarly sized but differently shaped hydrophobic cavities, we found a highly selective stabilization of the isomer whose shape matches that of the cavity of the cage. A Td-symmetric cage stabilized the spiropyrans’ colorless form and rendered them photochemically inert. In contrast, a D2h-symmetric cage favored the colored isomer, while maintaining reversible photoswitching between the two states of the encapsulated spiropyrans. We also show that the switching kinetics strongly depend on the substitution pattern on the spiropyran scaffold. This finding was used to fabricate a time-sensitive information storage medium with tunable lifetimes of the encoded messages."}],"extern":"1","title":"Altering the properties of spiropyran switches using coordination cages with different symmetries","status":"public","_id":"13348"},{"publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"quality_controlled":"1","month":"06","article_type":"original","type":"journal_article","external_id":{"pmid":["32469219"]},"doi":"10.1021/jacs.0c02848","volume":142,"publisher":"American Chemical Society","citation":{"short":"J.A. Malik, A. Madani, B. Pieber, P.H. Seeberger, Journal of the American Chemical Society 142 (2020) 11042–11049.","ama":"Malik JA, Madani A, Pieber B, Seeberger PH. Evidence for photocatalyst involvement in oxidative additions of nickel-catalyzed carboxylate O-arylations. <i>Journal of the American Chemical Society</i>. 2020;142(25):11042-11049. doi:<a href=\"https://doi.org/10.1021/jacs.0c02848\">10.1021/jacs.0c02848</a>","ista":"Malik JA, Madani A, Pieber B, Seeberger PH. 2020. Evidence for photocatalyst involvement in oxidative additions of nickel-catalyzed carboxylate O-arylations. Journal of the American Chemical Society. 142(25), 11042–11049.","chicago":"Malik, Jamal A., Amiera Madani, Bartholomäus Pieber, and Peter H. Seeberger. “Evidence for Photocatalyst Involvement in Oxidative Additions of Nickel-Catalyzed Carboxylate O-Arylations.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.0c02848\">https://doi.org/10.1021/jacs.0c02848</a>.","ieee":"J. A. Malik, A. Madani, B. Pieber, and P. H. Seeberger, “Evidence for photocatalyst involvement in oxidative additions of nickel-catalyzed carboxylate O-arylations,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 25. American Chemical Society, pp. 11042–11049, 2020.","mla":"Malik, Jamal A., et al. “Evidence for Photocatalyst Involvement in Oxidative Additions of Nickel-Catalyzed Carboxylate O-Arylations.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 25, American Chemical Society, 2020, pp. 11042–49, doi:<a href=\"https://doi.org/10.1021/jacs.0c02848\">10.1021/jacs.0c02848</a>.","apa":"Malik, J. A., Madani, A., Pieber, B., &#38; Seeberger, P. H. (2020). Evidence for photocatalyst involvement in oxidative additions of nickel-catalyzed carboxylate O-arylations. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.0c02848\">https://doi.org/10.1021/jacs.0c02848</a>"},"issue":"25","intvolume":"       142","day":"24","date_published":"2020-06-24T00:00:00Z","main_file_link":[{"url":"https://doi.org/10.1021/jacs.0c02848","open_access":"1"}],"article_processing_charge":"No","author":[{"full_name":"Malik, Jamal A.","first_name":"Jamal A.","last_name":"Malik"},{"full_name":"Madani, Amiera","last_name":"Madani","first_name":"Amiera"},{"full_name":"Pieber, Bartholomäus","first_name":"Bartholomäus","last_name":"Pieber","id":"93e5e5b2-0da6-11ed-8a41-af589a024726","orcid":"0000-0001-8689-388X"},{"last_name":"Seeberger","first_name":"Peter H.","full_name":"Seeberger, Peter H."}],"publication":"Journal of the American Chemical Society","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","language":[{"iso":"eng"}],"title":"Evidence for photocatalyst involvement in oxidative additions of nickel-catalyzed carboxylate O-arylations","status":"public","_id":"11978","abstract":[{"lang":"eng","text":"Dual photocatalysis and nickel catalysis can effect cross-coupling under mild conditions, but little is known about the in situ kinetics of this class of reactions. We report a comprehensive kinetic examination of a model carboxylate O-arylation, comparing a state-of-the-art homogeneous photocatalyst (Ir(ppy)3) with a competitive heterogeneous photocatalyst (graphitic carbon nitride). Experimental conditions were adjusted such that the nickel catalytic cycle is saturated with excited photocatalyst. This approach was designed to remove the role of the photocatalyst, by which only the intrinsic behaviors of the nickel catalytic cycles are observed. The two reactions did not display identical kinetics. Ir(ppy)3 deactivates the nickel catalytic cycle and creates more dehalogenated side product. Kinetic data for the reaction using Ir(ppy)3 supports a turnover-limiting reductive elimination. Graphitic carbon nitride gave higher selectivity, even at high photocatalyst-to-nickel ratios. The heterogeneous reaction also showed a rate dependence on aryl halide, indicating that oxidative addition plays a role in rate determination. The results argue against the current mechanistic hypothesis, which states that the photocatalyst is only involved to trigger reductive elimination."}],"date_created":"2022-08-25T10:57:38Z","oa":1,"extern":"1","pmid":1,"year":"2020","publication_status":"published","page":"11042-11049","oa_version":"Published Version","scopus_import":"1","date_updated":"2024-10-14T12:06:34Z"},{"title":"Modulating the optical properties of BODIPY dyes by noncovalent dimerization within a flexible coordination cage","status":"public","_id":"13362","abstract":[{"text":"Aggregation of organic molecules can drastically affect their physicochemical properties. For instance, the optical properties of BODIPY dyes are inherently related to the degree of aggregation and the mutual orientation of BODIPY units within these aggregates. Whereas the noncovalent aggregation of various BODIPY dyes has been studied in diverse media, the ill-defined nature of these aggregates has made it difficult to elucidate the structure–property relationships. Here, we studied the encapsulation of three structurally simple BODIPY derivatives within the hydrophobic cavity of a water-soluble, flexible PdII6L4 coordination cage. The cavity size allowed for the selective encapsulation of two dye molecules, irrespective of the substitution pattern on the BODIPY core. Working with a model, a pentamethyl-substituted derivative, we found that the mutual orientation of two BODIPY units in the cage’s cavity was remarkably similar to that in the crystalline state of the free dye, allowing us to isolate and characterize the smallest possible noncovalent H-type BODIPY aggregate, namely, an H-dimer. Interestingly, a CF3-substituted BODIPY, known for forming J-type aggregates, was also encapsulated as an H-dimer. Taking advantage of the dynamic nature of encapsulation, we developed a system in which reversible switching between H- and J-aggregates can be induced for multiple cycles simply by addition and subsequent destruction of the cage. We expect that the ability to rapidly and reversibly manipulate the optical properties of supramolecular inclusion complexes in aqueous media will open up avenues for developing detection systems that operate within biological environments.","lang":"eng"}],"date_created":"2023-08-01T09:36:10Z","oa":1,"extern":"1","oa_version":"Published Version","scopus_import":"1","date_updated":"2024-10-14T12:12:41Z","pmid":1,"year":"2020","publication_status":"published","page":"17721-17729","type":"journal_article","external_id":{"pmid":["33006898"]},"doi":"10.1021/jacs.0c08589","volume":142,"publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"quality_controlled":"1","month":"10","article_type":"original","author":[{"first_name":"Julius","last_name":"Gemen","full_name":"Gemen, Julius"},{"full_name":"Ahrens, Johannes","first_name":"Johannes","last_name":"Ahrens"},{"first_name":"Linda J. W.","last_name":"Shimon","full_name":"Shimon, Linda J. W."},{"id":"8e84690e-1e48-11ed-a02b-a1e6fb8bb53b","full_name":"Klajn, Rafal","first_name":"Rafal","last_name":"Klajn"}],"publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"publisher":"American Chemical Society","citation":{"apa":"Gemen, J., Ahrens, J., Shimon, L. J. W., &#38; Klajn, R. (2020). Modulating the optical properties of BODIPY dyes by noncovalent dimerization within a flexible coordination cage. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.0c08589\">https://doi.org/10.1021/jacs.0c08589</a>","mla":"Gemen, Julius, et al. “Modulating the Optical Properties of BODIPY Dyes by Noncovalent Dimerization within a Flexible Coordination Cage.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 41, American Chemical Society, 2020, pp. 17721–29, doi:<a href=\"https://doi.org/10.1021/jacs.0c08589\">10.1021/jacs.0c08589</a>.","ieee":"J. Gemen, J. Ahrens, L. J. W. Shimon, and R. Klajn, “Modulating the optical properties of BODIPY dyes by noncovalent dimerization within a flexible coordination cage,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 41. American Chemical Society, pp. 17721–17729, 2020.","chicago":"Gemen, Julius, Johannes Ahrens, Linda J. W. Shimon, and Rafal Klajn. “Modulating the Optical Properties of BODIPY Dyes by Noncovalent Dimerization within a Flexible Coordination Cage.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.0c08589\">https://doi.org/10.1021/jacs.0c08589</a>.","ista":"Gemen J, Ahrens J, Shimon LJW, Klajn R. 2020. Modulating the optical properties of BODIPY dyes by noncovalent dimerization within a flexible coordination cage. Journal of the American Chemical Society. 142(41), 17721–17729.","ama":"Gemen J, Ahrens J, Shimon LJW, Klajn R. Modulating the optical properties of BODIPY dyes by noncovalent dimerization within a flexible coordination cage. <i>Journal of the American Chemical Society</i>. 2020;142(41):17721-17729. doi:<a href=\"https://doi.org/10.1021/jacs.0c08589\">10.1021/jacs.0c08589</a>","short":"J. Gemen, J. Ahrens, L.J.W. Shimon, R. Klajn, Journal of the American Chemical Society 142 (2020) 17721–17729."},"issue":"41","intvolume":"       142","main_file_link":[{"url":"https://doi.org/10.1021/jacs.0c08589","open_access":"1"}],"date_published":"2020-10-04T00:00:00Z","day":"04","article_processing_charge":"No"},{"intvolume":"       142","issue":"34","citation":{"short":"M. Canton, A.B. Grommet, L. Pesce, J. Gemen, S. Li, Y. Diskin-Posner, A. Credi, G.M. Pavan, J. Andréasson, R. Klajn, Journal of the American Chemical Society 142 (2020) 14557–14565.","ama":"Canton M, Grommet AB, Pesce L, et al. Improving fatigue resistance of dihydropyrene by encapsulation within a coordination cage. <i>Journal of the American Chemical Society</i>. 2020;142(34):14557-14565. doi:<a href=\"https://doi.org/10.1021/jacs.0c06146\">10.1021/jacs.0c06146</a>","chicago":"Canton, Martina, Angela B. Grommet, Luca Pesce, Julius Gemen, Shiming Li, Yael Diskin-Posner, Alberto Credi, Giovanni M. Pavan, Joakim Andréasson, and Rafal Klajn. “Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.0c06146\">https://doi.org/10.1021/jacs.0c06146</a>.","ieee":"M. Canton <i>et al.</i>, “Improving fatigue resistance of dihydropyrene by encapsulation within a coordination cage,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 34. American Chemical Society, pp. 14557–14565, 2020.","ista":"Canton M, Grommet AB, Pesce L, Gemen J, Li S, Diskin-Posner Y, Credi A, Pavan GM, Andréasson J, Klajn R. 2020. Improving fatigue resistance of dihydropyrene by encapsulation within a coordination cage. Journal of the American Chemical Society. 142(34), 14557–14565.","mla":"Canton, Martina, et al. “Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 34, American Chemical Society, 2020, pp. 14557–65, doi:<a href=\"https://doi.org/10.1021/jacs.0c06146\">10.1021/jacs.0c06146</a>.","apa":"Canton, M., Grommet, A. B., Pesce, L., Gemen, J., Li, S., Diskin-Posner, Y., … Klajn, R. (2020). Improving fatigue resistance of dihydropyrene by encapsulation within a coordination cage. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.0c06146\">https://doi.org/10.1021/jacs.0c06146</a>"},"publisher":"American Chemical Society","article_processing_charge":"No","main_file_link":[{"open_access":"1","url":"https://doi.org/10.1021/jacs.0c06146"}],"day":"14","date_published":"2020-08-14T00:00:00Z","author":[{"full_name":"Canton, Martina","first_name":"Martina","last_name":"Canton"},{"last_name":"Grommet","first_name":"Angela B.","full_name":"Grommet, Angela B."},{"last_name":"Pesce","first_name":"Luca","full_name":"Pesce, Luca"},{"first_name":"Julius","last_name":"Gemen","full_name":"Gemen, Julius"},{"first_name":"Shiming","last_name":"Li","full_name":"Li, Shiming"},{"full_name":"Diskin-Posner, Yael","first_name":"Yael","last_name":"Diskin-Posner"},{"first_name":"Alberto","last_name":"Credi","full_name":"Credi, Alberto"},{"full_name":"Pavan, Giovanni M.","first_name":"Giovanni M.","last_name":"Pavan"},{"last_name":"Andréasson","first_name":"Joakim","full_name":"Andréasson, Joakim"},{"first_name":"Rafal","last_name":"Klajn","full_name":"Klajn, Rafal","id":"8e84690e-1e48-11ed-a02b-a1e6fb8bb53b"}],"keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","language":[{"iso":"eng"}],"publication":"Journal of the American Chemical Society","publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"article_type":"original","month":"08","quality_controlled":"1","external_id":{"pmid":["32791832"]},"type":"journal_article","volume":142,"doi":"10.1021/jacs.0c06146","year":"2020","pmid":1,"publication_status":"published","page":"14557-14565","scopus_import":"1","oa_version":"Published Version","date_updated":"2023-08-07T10:15:38Z","_id":"13364","status":"public","title":"Improving fatigue resistance of dihydropyrene by encapsulation within a coordination cage","extern":"1","oa":1,"date_created":"2023-08-01T09:36:59Z","abstract":[{"text":"Photochromic molecules undergo reversible isomerization upon irradiation with light at different wavelengths, a process that can alter their physical and chemical properties. For instance, dihydropyrene (DHP) is a deep-colored compound that isomerizes to light-brown cyclophanediene (CPD) upon irradiation with visible light. CPD can then isomerize back to DHP upon irradiation with UV light or thermally in the dark. Conversion between DHP and CPD is thought to proceed via a biradical intermediate; bimolecular events involving this unstable intermediate thus result in rapid decomposition and poor cycling performance. Here, we show that the reversible isomerization of DHP can be stabilized upon confinement within a PdII6L4 coordination cage. By protecting this reactive intermediate using the cage, each isomerization reaction proceeds to higher yield, which significantly decreases the fatigue experienced by the system upon repeated photocycling. Although molecular confinement is known to help stabilize reactive species, this effect is not typically employed to protect reactive intermediates and thus improve reaction yields. We envisage that performing reactions under confinement will not only improve the cyclic performance of photochromic molecules, but may also increase the amount of product obtainable from traditionally low-yielding organic reactions.","lang":"eng"}]},{"date_updated":"2023-08-07T10:18:53Z","oa_version":"Published Version","scopus_import":"1","page":"9792-9802","publication_status":"published","pmid":1,"year":"2020","oa":1,"date_created":"2023-08-01T09:37:12Z","abstract":[{"lang":"eng","text":"Photoswitchable molecules are employed for many applications, from the development of active materials to the design of stimuli-responsive molecular systems and light-powered molecular machines. To fully exploit their potential, we must learn ways to control the mechanism and kinetics of their photoinduced isomerization. One possible strategy involves confinement of photoresponsive switches such as azobenzenes or spiropyrans within crowded molecular environments, which may allow control over their light-induced conversion. However, the molecular factors that influence and control the switching process under realistic conditions and within dynamic molecular regimes often remain difficult to ascertain. As a case study, here we have employed molecular models to probe the isomerization of azobenzene guests within a Pd(II)-based coordination cage host in water. Atomistic molecular dynamics and metadynamics simulations allow us to characterize the flexibility of the cage in the solvent, the (rare) guest encapsulation and release events, and the relative probability/kinetics of light-induced isomerization of azobenzene analogues in these host–guest systems. In this way, we can reconstruct the mechanism of azobenzene switching inside the cage cavity and explore key molecular factors that may control this event. We obtain a molecular-level insight on the effects of crowding and host–guest interactions on azobenzene isomerization. The detailed picture elucidated by this study may enable the rational design of photoswitchable systems whose reactivity can be controlled via host–guest interactions."}],"extern":"1","title":"Molecular factors controlling the isomerization of Azobenzenes in the cavity of a flexible coordination cage","status":"public","_id":"13365","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","language":[{"iso":"eng"}],"publication":"Journal of the American Chemical Society","keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"author":[{"last_name":"Pesce","first_name":"Luca","full_name":"Pesce, Luca"},{"full_name":"Perego, Claudio","last_name":"Perego","first_name":"Claudio"},{"first_name":"Angela B.","last_name":"Grommet","full_name":"Grommet, Angela B."},{"full_name":"Klajn, Rafal","last_name":"Klajn","first_name":"Rafal","id":"8e84690e-1e48-11ed-a02b-a1e6fb8bb53b"},{"first_name":"Giovanni M.","last_name":"Pavan","full_name":"Pavan, Giovanni M."}],"article_processing_charge":"No","day":"30","main_file_link":[{"url":"https://doi.org/10.1021/jacs.0c03444","open_access":"1"}],"date_published":"2020-04-30T00:00:00Z","citation":{"short":"L. Pesce, C. Perego, A.B. Grommet, R. Klajn, G.M. Pavan, Journal of the American Chemical Society 142 (2020) 9792–9802.","ama":"Pesce L, Perego C, Grommet AB, Klajn R, Pavan GM. Molecular factors controlling the isomerization of Azobenzenes in the cavity of a flexible coordination cage. <i>Journal of the American Chemical Society</i>. 2020;142(21):9792-9802. doi:<a href=\"https://doi.org/10.1021/jacs.0c03444\">10.1021/jacs.0c03444</a>","chicago":"Pesce, Luca, Claudio Perego, Angela B. Grommet, Rafal Klajn, and Giovanni M. Pavan. “Molecular Factors Controlling the Isomerization of Azobenzenes in the Cavity of a Flexible Coordination Cage.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.0c03444\">https://doi.org/10.1021/jacs.0c03444</a>.","ieee":"L. Pesce, C. Perego, A. B. Grommet, R. Klajn, and G. M. Pavan, “Molecular factors controlling the isomerization of Azobenzenes in the cavity of a flexible coordination cage,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 21. American Chemical Society, pp. 9792–9802, 2020.","ista":"Pesce L, Perego C, Grommet AB, Klajn R, Pavan GM. 2020. Molecular factors controlling the isomerization of Azobenzenes in the cavity of a flexible coordination cage. Journal of the American Chemical Society. 142(21), 9792–9802.","mla":"Pesce, Luca, et al. “Molecular Factors Controlling the Isomerization of Azobenzenes in the Cavity of a Flexible Coordination Cage.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 21, American Chemical Society, 2020, pp. 9792–802, doi:<a href=\"https://doi.org/10.1021/jacs.0c03444\">10.1021/jacs.0c03444</a>.","apa":"Pesce, L., Perego, C., Grommet, A. B., Klajn, R., &#38; Pavan, G. M. (2020). Molecular factors controlling the isomerization of Azobenzenes in the cavity of a flexible coordination cage. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.0c03444\">https://doi.org/10.1021/jacs.0c03444</a>"},"publisher":"American Chemical Society","intvolume":"       142","issue":"21","volume":142,"doi":"10.1021/jacs.0c03444","external_id":{"pmid":["32353237"]},"type":"journal_article","month":"04","quality_controlled":"1","article_type":"original","publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]}},{"title":"Overcoming selectivity issues in reversible catalysis: A transfer hydrocyanation exhibiting high kinetic control","status":"public","_id":"20766","abstract":[{"text":"Reversible catalytic reactions operate under thermodynamic control, and thus, establishing a selective catalytic system poses a considerable challenge. Herein, we report a reversible transfer hydrocyanation protocol that exhibits high selectivity for the thermodynamically less favorable branched isomer. Selectivity is achieved by exploiting the lower barrier for C–CN oxidative addition and reductive elimination at benzylic positions in the absence of a cocatalytic Lewis acid. Through the design of a novel type of HCN donor, a practical, branched-selective, HCN-free transfer hydrocyanation was realized. The synthetically useful resolution of a mixture of branched and linear nitrile isomers was also demonstrated to underline the value of reversible and selective transfer reactions. In a broader context, this work demonstrates that high kinetic selectivity can be achieved in reversible transfer reactions, thus opening new horizons for their synthetic applications.","lang":"eng"}],"oa":1,"date_created":"2025-12-09T14:25:37Z","extern":"1","oa_version":"Preprint","scopus_import":"1","date_updated":"2025-12-16T12:10:08Z","pmid":1,"year":"2020","publication_status":"published","page":"10914-10920","OA_type":"green","type":"journal_article","external_id":{"pmid":["32478515"]},"doi":"10.1021/jacs.0c03184","volume":142,"publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"quality_controlled":"1","month":"06","article_type":"original","author":[{"full_name":"Bhawal, Benjamin N.","first_name":"Benjamin N.","last_name":"Bhawal"},{"last_name":"Reisenbauer","first_name":"Julia","full_name":"Reisenbauer, Julia","id":"51d862e9-36ee-11f0-86d3-8534c85a5496"},{"last_name":"Ehinger","first_name":"Christian","full_name":"Ehinger, Christian"},{"full_name":"Morandi, Bill","last_name":"Morandi","first_name":"Bill"}],"OA_place":"repository","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","language":[{"iso":"eng"}],"publication":"Journal of the American Chemical Society","publisher":"American Chemical Society","citation":{"chicago":"Bhawal, Benjamin N., Julia Reisenbauer, Christian Ehinger, and Bill Morandi. “Overcoming Selectivity Issues in Reversible Catalysis: A Transfer Hydrocyanation Exhibiting High Kinetic Control.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.0c03184\">https://doi.org/10.1021/jacs.0c03184</a>.","ieee":"B. N. Bhawal, J. Reisenbauer, C. Ehinger, and B. Morandi, “Overcoming selectivity issues in reversible catalysis: A transfer hydrocyanation exhibiting high kinetic control,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 25. American Chemical Society, pp. 10914–10920, 2020.","ista":"Bhawal BN, Reisenbauer J, Ehinger C, Morandi B. 2020. Overcoming selectivity issues in reversible catalysis: A transfer hydrocyanation exhibiting high kinetic control. Journal of the American Chemical Society. 142(25), 10914–10920.","ama":"Bhawal BN, Reisenbauer J, Ehinger C, Morandi B. Overcoming selectivity issues in reversible catalysis: A transfer hydrocyanation exhibiting high kinetic control. <i>Journal of the American Chemical Society</i>. 2020;142(25):10914-10920. doi:<a href=\"https://doi.org/10.1021/jacs.0c03184\">10.1021/jacs.0c03184</a>","short":"B.N. Bhawal, J. Reisenbauer, C. Ehinger, B. Morandi, Journal of the American Chemical Society 142 (2020) 10914–10920.","apa":"Bhawal, B. N., Reisenbauer, J., Ehinger, C., &#38; Morandi, B. (2020). Overcoming selectivity issues in reversible catalysis: A transfer hydrocyanation exhibiting high kinetic control. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.0c03184\">https://doi.org/10.1021/jacs.0c03184</a>","mla":"Bhawal, Benjamin N., et al. “Overcoming Selectivity Issues in Reversible Catalysis: A Transfer Hydrocyanation Exhibiting High Kinetic Control.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 25, American Chemical Society, 2020, pp. 10914–20, doi:<a href=\"https://doi.org/10.1021/jacs.0c03184\">10.1021/jacs.0c03184</a>."},"issue":"25","intvolume":"       142","main_file_link":[{"url":"10.26434/chemrxiv.11931633.v1","open_access":"1"}],"day":"01","date_published":"2020-06-01T00:00:00Z","article_processing_charge":"No"},{"external_id":{"pmid":["33175526"]},"type":"journal_article","volume":142,"doi":"10.1021/jacs.0c10743","publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"month":"11","quality_controlled":"1","article_type":"letter_note","author":[{"last_name":"Doud","first_name":"Evan A.","full_name":"Doud, Evan A."},{"first_name":"Rachel L.","last_name":"Starr","full_name":"Starr, Rachel L."},{"full_name":"Kladnik, Gregor","first_name":"Gregor","last_name":"Kladnik"},{"full_name":"Voevodin, Anastasia","first_name":"Anastasia","last_name":"Voevodin"},{"first_name":"Enrique","last_name":"Montes","full_name":"Montes, Enrique"},{"last_name":"Arasu","first_name":"Narendra P.","full_name":"Arasu, Narendra P."},{"last_name":"Zang","first_name":"Yaping","full_name":"Zang, Yaping"},{"full_name":"Zahl, Percy","first_name":"Percy","last_name":"Zahl"},{"full_name":"Morgante, Alberto","first_name":"Alberto","last_name":"Morgante"},{"full_name":"Venkataraman, Latha","last_name":"Venkataraman","first_name":"Latha","id":"9ebb78a5-cc0d-11ee-8322-fae086a32caf","orcid":"0000-0002-6957-6089"},{"full_name":"Vázquez, Héctor","first_name":"Héctor","last_name":"Vázquez"},{"full_name":"Cvetko, Dean","last_name":"Cvetko","first_name":"Dean"},{"full_name":"Roy, Xavier","first_name":"Xavier","last_name":"Roy"}],"publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","citation":{"mla":"Doud, Evan A., et al. “Cyclopropenylidenes as Strong Carbene Anchoring Groups on Au Surfaces.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 47, American Chemical Society, 2020, pp. 19902–06, doi:<a href=\"https://doi.org/10.1021/jacs.0c10743\">10.1021/jacs.0c10743</a>.","apa":"Doud, E. A., Starr, R. L., Kladnik, G., Voevodin, A., Montes, E., Arasu, N. P., … Roy, X. (2020). Cyclopropenylidenes as strong carbene anchoring groups on Au surfaces. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.0c10743\">https://doi.org/10.1021/jacs.0c10743</a>","short":"E.A. Doud, R.L. Starr, G. Kladnik, A. Voevodin, E. Montes, N.P. Arasu, Y. Zang, P. Zahl, A. Morgante, L. Venkataraman, H. Vázquez, D. Cvetko, X. Roy, Journal of the American Chemical Society 142 (2020) 19902–19906.","ama":"Doud EA, Starr RL, Kladnik G, et al. Cyclopropenylidenes as strong carbene anchoring groups on Au surfaces. <i>Journal of the American Chemical Society</i>. 2020;142(47):19902-19906. doi:<a href=\"https://doi.org/10.1021/jacs.0c10743\">10.1021/jacs.0c10743</a>","ista":"Doud EA, Starr RL, Kladnik G, Voevodin A, Montes E, Arasu NP, Zang Y, Zahl P, Morgante A, Venkataraman L, Vázquez H, Cvetko D, Roy X. 2020. Cyclopropenylidenes as strong carbene anchoring groups on Au surfaces. Journal of the American Chemical Society. 142(47), 19902–19906.","chicago":"Doud, Evan A., Rachel L. Starr, Gregor Kladnik, Anastasia Voevodin, Enrique Montes, Narendra P. Arasu, Yaping Zang, et al. “Cyclopropenylidenes as Strong Carbene Anchoring Groups on Au Surfaces.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.0c10743\">https://doi.org/10.1021/jacs.0c10743</a>.","ieee":"E. A. Doud <i>et al.</i>, “Cyclopropenylidenes as strong carbene anchoring groups on Au surfaces,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 47. American Chemical Society, pp. 19902–19906, 2020."},"publisher":"American Chemical Society","intvolume":"       142","issue":"47","article_processing_charge":"No","date_published":"2020-11-11T00:00:00Z","day":"11","title":"Cyclopropenylidenes as strong carbene anchoring groups on Au surfaces","status":"public","_id":"17904","date_created":"2024-09-09T07:13:45Z","abstract":[{"lang":"eng","text":"The creation of stable molecular monolayers on metallic surfaces is a fundamental challenge of surface chemistry. N-Heterocyclic carbenes (NHCs) were recently shown to form self-assembled monolayers that are significantly more stable than the traditional thiols on Au system. Here we theoretically and experimentally demonstrate that the smallest cyclic carbene, cyclopropenylidene, binds even more strongly than NHCs to Au surfaces without altering the surface structure. We deposit bis(diisopropylamino)cyclopropenylidene (BAC) on Au(111) using the molecular adduct BAC–CO2 as a precursor and determine the structure, geometry, and behavior of the surface-bound molecules through high-resolution X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy. Our experiments are supported by density functional theory calculations of the molecular binding energy of BAC on Au(111) and its electronic structure. Our work is the first demonstration of surface modification with a stable carbene other than NHC; more broadly, it drives further exploration of various carbenes on metal surfaces."}],"extern":"1","oa_version":"None","scopus_import":"1","date_updated":"2024-12-10T10:34:58Z","pmid":1,"year":"2020","OA_type":"closed access","page":"19902-19906","publication_status":"published"},{"pmid":1,"year":"2020","publication_status":"published","page":"14924-14932","OA_type":"closed access","oa_version":"None","scopus_import":"1","date_updated":"2024-12-10T12:04:31Z","title":"Single-electron currents in designer single-cluster devices","status":"public","_id":"17909","abstract":[{"lang":"eng","text":"Atomically precise clusters can be used to create single-electron devices wherein a single redox-active cluster is connected to two macroscopic electrodes via anchoring ligands. Unlike single-electron devices comprising nanocrystals, these cluster-based devices can be fabricated with atomic precision. This affords an unprecedented level of control over the device properties. Herein, we design a series of cobalt chalcogenide clusters with varying ligand geometries and core nuclearities to control their current–voltage (I–V) characteristics in a scanning tunneling microscope-based break junction (STM-BJ) device. First, the device geometry is modified by precisely positioning junction-anchoring ligands on the surface of the cluster. We show that the I–V characteristics are independent of ligand placement, confirming a sequential, single-electron tunneling mechanism. Next, we chemically fuse two clusters to realize a larger cluster dimer that behaves as a single electronic unit, possessing a smaller reorganization energy and more accessible redox states than the monomeric analogues. As a result, dimer-based devices exhibit significantly higher currents and can even be pushed to current saturation at high bias. Owing to these controllable properties, single-cluster junctions serve as an excellent platform for exploring incoherent charge transport processes at the nanoscale. With this understanding, as well as properties such as nonlinear I–V characteristics and rectification, these molecular clusters may function as conductive inorganic nodes in new devices and materials."}],"date_created":"2024-09-09T07:19:56Z","extern":"1","publisher":"American Chemical Society","citation":{"mla":"Gunasekaran, Suman, et al. “Single-Electron Currents in Designer Single-Cluster Devices.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 35, American Chemical Society, 2020, pp. 14924–32, doi:<a href=\"https://doi.org/10.1021/jacs.0c04970\">10.1021/jacs.0c04970</a>.","apa":"Gunasekaran, S., Reed, D. A., Paley, D. W., Bartholomew, A. K., Venkataraman, L., Steigerwald, M. L., … Nuckolls, C. (2020). Single-electron currents in designer single-cluster devices. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.0c04970\">https://doi.org/10.1021/jacs.0c04970</a>","ama":"Gunasekaran S, Reed DA, Paley DW, et al. Single-electron currents in designer single-cluster devices. <i>Journal of the American Chemical Society</i>. 2020;142(35):14924-14932. doi:<a href=\"https://doi.org/10.1021/jacs.0c04970\">10.1021/jacs.0c04970</a>","ista":"Gunasekaran S, Reed DA, Paley DW, Bartholomew AK, Venkataraman L, Steigerwald ML, Roy X, Nuckolls C. 2020. Single-electron currents in designer single-cluster devices. Journal of the American Chemical Society. 142(35), 14924–14932.","ieee":"S. Gunasekaran <i>et al.</i>, “Single-electron currents in designer single-cluster devices,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 35. American Chemical Society, pp. 14924–14932, 2020.","chicago":"Gunasekaran, Suman, Douglas A. Reed, Daniel W. Paley, Amymarie K. Bartholomew, Latha Venkataraman, Michael L. Steigerwald, Xavier Roy, and Colin Nuckolls. “Single-Electron Currents in Designer Single-Cluster Devices.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.0c04970\">https://doi.org/10.1021/jacs.0c04970</a>.","short":"S. Gunasekaran, D.A. Reed, D.W. Paley, A.K. Bartholomew, L. Venkataraman, M.L. Steigerwald, X. Roy, C. Nuckolls, Journal of the American Chemical Society 142 (2020) 14924–14932."},"issue":"35","intvolume":"       142","date_published":"2020-08-18T00:00:00Z","day":"18","article_processing_charge":"No","author":[{"full_name":"Gunasekaran, Suman","last_name":"Gunasekaran","first_name":"Suman"},{"first_name":"Douglas A.","last_name":"Reed","full_name":"Reed, Douglas A."},{"full_name":"Paley, Daniel W.","last_name":"Paley","first_name":"Daniel W."},{"full_name":"Bartholomew, Amymarie K.","last_name":"Bartholomew","first_name":"Amymarie K."},{"id":"9ebb78a5-cc0d-11ee-8322-fae086a32caf","orcid":"0000-0002-6957-6089","full_name":"Venkataraman, Latha","first_name":"Latha","last_name":"Venkataraman"},{"last_name":"Steigerwald","first_name":"Michael L.","full_name":"Steigerwald, Michael L."},{"full_name":"Roy, Xavier","last_name":"Roy","first_name":"Xavier"},{"full_name":"Nuckolls, Colin","last_name":"Nuckolls","first_name":"Colin"}],"language":[{"iso":"eng"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication":"Journal of the American Chemical Society","publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"quality_controlled":"1","month":"08","article_type":"original","type":"journal_article","external_id":{"pmid":["32809814"]},"doi":"10.1021/jacs.0c04970","volume":142},{"day":"26","date_published":"2020-03-26T00:00:00Z","article_processing_charge":"No","issue":"15","intvolume":"       142","publisher":"American Chemical Society","citation":{"mla":"Starr, Rachel L., et al. “Gold–Carbon Contacts from Oxidative Addition of Aryl Iodides.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 15, American Chemical Society, 2020, pp. 7128–33, doi:<a href=\"https://doi.org/10.1021/jacs.0c01466\">10.1021/jacs.0c01466</a>.","apa":"Starr, R. L., Fu, T., Doud, E. A., Stone, I., Roy, X., &#38; Venkataraman, L. (2020). Gold–carbon contacts from oxidative addition of aryl iodides. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.0c01466\">https://doi.org/10.1021/jacs.0c01466</a>","short":"R.L. Starr, T. Fu, E.A. Doud, I. Stone, X. Roy, L. Venkataraman, Journal of the American Chemical Society 142 (2020) 7128–7133.","ama":"Starr RL, Fu T, Doud EA, Stone I, Roy X, Venkataraman L. Gold–carbon contacts from oxidative addition of aryl iodides. <i>Journal of the American Chemical Society</i>. 2020;142(15):7128-7133. doi:<a href=\"https://doi.org/10.1021/jacs.0c01466\">10.1021/jacs.0c01466</a>","ieee":"R. L. Starr, T. Fu, E. A. Doud, I. Stone, X. Roy, and L. Venkataraman, “Gold–carbon contacts from oxidative addition of aryl iodides,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 15. American Chemical Society, pp. 7128–7133, 2020.","ista":"Starr RL, Fu T, Doud EA, Stone I, Roy X, Venkataraman L. 2020. Gold–carbon contacts from oxidative addition of aryl iodides. Journal of the American Chemical Society. 142(15), 7128–7133.","chicago":"Starr, Rachel L., Tianren Fu, Evan A. Doud, Ilana Stone, Xavier Roy, and Latha Venkataraman. “Gold–Carbon Contacts from Oxidative Addition of Aryl Iodides.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.0c01466\">https://doi.org/10.1021/jacs.0c01466</a>."},"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"author":[{"last_name":"Starr","first_name":"Rachel L.","full_name":"Starr, Rachel L."},{"first_name":"Tianren","last_name":"Fu","full_name":"Fu, Tianren"},{"full_name":"Doud, Evan A.","first_name":"Evan A.","last_name":"Doud"},{"full_name":"Stone, Ilana","last_name":"Stone","first_name":"Ilana"},{"full_name":"Roy, Xavier","first_name":"Xavier","last_name":"Roy"},{"id":"9ebb78a5-cc0d-11ee-8322-fae086a32caf","orcid":"0000-0002-6957-6089","full_name":"Venkataraman, Latha","last_name":"Venkataraman","first_name":"Latha"}],"article_type":"original","quality_controlled":"1","month":"03","publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"doi":"10.1021/jacs.0c01466","volume":142,"type":"journal_article","external_id":{"pmid":["32212683"]},"publication_status":"published","page":"7128-7133","OA_type":"closed access","year":"2020","pmid":1,"date_updated":"2024-12-10T12:20:47Z","scopus_import":"1","oa_version":"None","extern":"1","abstract":[{"lang":"eng","text":"Aryl halides are ubiquitous functional groups in organic chemistry, yet despite their obvious appeal as surface-binding linkers and as precursors for controlled graphene nanoribbon synthesis, they have seldom been used as such in molecular electronics. The confusion regarding the bonding of aryl iodides to Au electrodes is a case in point, with ambiguous reports of both dative Au–I and covalent Au–C contacts. Here we form single-molecule junctions with a series of oligophenylene molecular wires terminated asymmetrically with iodine and thiomethyl to show that the dative Au–I contact has a lower conductance than the covalent Au–C interaction, which we propose occurs via an in situ oxidative addition reaction at the Au surface. Furthermore, we confirm the formation of the Au–C bond by measuring an analogous series of molecules prepared ex situ with the complex AuI(PPh3) in place of the iodide. Density functional theory-based transport calculations support our experimental observations that Au–C linkages have higher conductance than Au–I linkages. Finally, we demonstrate selective promotion of the Au–C bond formation by controlling the bias applied across the junction. In addition to establishing the different binding modes of aryl iodides, our results chart a path to actively controlling oxidative addition on an Au surface using an applied bias."}],"date_created":"2024-09-09T07:22:26Z","_id":"17912","status":"public","title":"Gold–carbon contacts from oxidative addition of aryl iodides"},{"year":"2020","pmid":1,"publication_status":"published","page":"9220-9230","oa_version":"None","scopus_import":"1","date_updated":"2026-07-06T12:16:34Z","_id":"8040","status":"public","title":"Charge transfer and chemo-mechanical coupling in respiratory complex I","abstract":[{"lang":"eng","text":"The mitochondrial respiratory chain, formed by five protein complexes, utilizes energy from catabolic processes to synthesize ATP. Complex I, the first and the largest protein complex of the chain, harvests electrons from NADH to reduce quinone, while pumping protons across the mitochondrial membrane. Detailed knowledge of the working principle of such coupled charge-transfer processes remains, however, fragmentary due to bottlenecks in understanding redox-driven conformational transitions and their interplay with the hydrated proton pathways. Complex I from Thermus thermophilus encases 16 subunits with nine iron–sulfur clusters, reduced by electrons from NADH. Here, employing the latest crystal structure of T. thermophilus complex I, we have used microsecond-scale molecular dynamics simulations to study the chemo-mechanical coupling between redox changes of the iron–sulfur clusters and conformational transitions across complex I. First, we identify the redox switches within complex I, which allosterically couple the dynamics of the quinone binding pocket to the site of NADH reduction. Second, our free-energy calculations reveal that the affinity of the quinone, specifically menaquinone, for the binding-site is higher than that of its reduced, menaquinol form—a design essential for menaquinol release. Remarkably, the barriers to diffusive menaquinone dynamics are lesser than that of the more ubiquitous ubiquinone, and the naphthoquinone headgroup of the former furnishes stronger binding interactions with the pocket, favoring menaquinone for charge transport in T. thermophilus. Our computations are consistent with experimentally validated mutations and hierarchize the key residues into three functional classes, identifying new mutation targets. Third, long-range hydrogen-bond networks connecting the quinone-binding site to the transmembrane subunits are found to be responsible for proton pumping. Put together, the simulations reveal the molecular design principles linking redox reactions to quinone turnover to proton translocation in complex I."}],"date_created":"2020-06-29T07:59:35Z","corr_author":"1","isi":1,"issue":"20","intvolume":"       142","publisher":"American Chemical Society","citation":{"mla":"Gupta, Chitrak, et al. “Charge Transfer and Chemo-Mechanical Coupling in Respiratory Complex I.” <i>Journal of the American Chemical Society</i>, vol. 142, no. 20, American Chemical Society, 2020, pp. 9220–30, doi:<a href=\"https://doi.org/10.1021/jacs.9b13450\">10.1021/jacs.9b13450</a>.","apa":"Gupta, C., Khaniya, U., Chan, C. K., Dehez, F., Shekhar, M., Gunner, M. R., … Singharoy, A. (2020). Charge transfer and chemo-mechanical coupling in respiratory complex I. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.9b13450\">https://doi.org/10.1021/jacs.9b13450</a>","ama":"Gupta C, Khaniya U, Chan CK, et al. Charge transfer and chemo-mechanical coupling in respiratory complex I. <i>Journal of the American Chemical Society</i>. 2020;142(20):9220-9230. doi:<a href=\"https://doi.org/10.1021/jacs.9b13450\">10.1021/jacs.9b13450</a>","ista":"Gupta C, Khaniya U, Chan CK, Dehez F, Shekhar M, Gunner MR, Sazanov LA, Chipot C, Singharoy A. 2020. Charge transfer and chemo-mechanical coupling in respiratory complex I. Journal of the American Chemical Society. 142(20), 9220–9230.","ieee":"C. Gupta <i>et al.</i>, “Charge transfer and chemo-mechanical coupling in respiratory complex I,” <i>Journal of the American Chemical Society</i>, vol. 142, no. 20. American Chemical Society, pp. 9220–9230, 2020.","chicago":"Gupta, Chitrak, Umesh Khaniya, Chun Kit Chan, Francois Dehez, Mrinal Shekhar, M. R. Gunner, Leonid A Sazanov, Christophe Chipot, and Abhishek Singharoy. “Charge Transfer and Chemo-Mechanical Coupling in Respiratory Complex I.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/jacs.9b13450\">https://doi.org/10.1021/jacs.9b13450</a>.","short":"C. Gupta, U. Khaniya, C.K. Chan, F. Dehez, M. Shekhar, M.R. Gunner, L.A. Sazanov, C. Chipot, A. Singharoy, Journal of the American Chemical Society 142 (2020) 9220–9230."},"day":"20","date_published":"2020-05-20T00:00:00Z","article_processing_charge":"No","related_material":{"record":[{"id":"9878","status":"public","relation":"research_data"},{"relation":"research_data","status":"public","id":"9326"},{"id":"9713","status":"public","relation":"research_data"}]},"department":[{"_id":"LeSa"}],"author":[{"last_name":"Gupta","first_name":"Chitrak","full_name":"Gupta, Chitrak"},{"full_name":"Khaniya, Umesh","first_name":"Umesh","last_name":"Khaniya"},{"full_name":"Chan, Chun Kit","first_name":"Chun Kit","last_name":"Chan"},{"full_name":"Dehez, Francois","first_name":"Francois","last_name":"Dehez"},{"first_name":"Mrinal","last_name":"Shekhar","full_name":"Shekhar, Mrinal"},{"full_name":"Gunner, M. R.","last_name":"Gunner","first_name":"M. R."},{"full_name":"Sazanov, Leonid A","first_name":"Leonid A","last_name":"Sazanov","id":"338D39FE-F248-11E8-B48F-1D18A9856A87","orcid":"0000-0002-0977-7989"},{"first_name":"Christophe","last_name":"Chipot","full_name":"Chipot, Christophe"},{"full_name":"Singharoy, Abhishek","last_name":"Singharoy","first_name":"Abhishek"}],"language":[{"iso":"eng"}],"publication":"Journal of the American Chemical Society","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"article_type":"original","quality_controlled":"1","month":"05","type":"journal_article","external_id":{"isi":["000537415600020"],"pmid":["32347721"]},"doi":"10.1021/jacs.9b13450","volume":142},{"publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"month":"02","quality_controlled":"1","article_type":"original","external_id":{"pmid":["30595017"]},"type":"journal_article","volume":141,"doi":"10.1021/jacs.8b09638","citation":{"ama":"Chu Z, Han Y, Bian T, De S, Král P, Klajn R. Supramolecular control of azobenzene switching on nanoparticles. <i>Journal of the American Chemical Society</i>. 2019;141(5):1949-1960. doi:<a href=\"https://doi.org/10.1021/jacs.8b09638\">10.1021/jacs.8b09638</a>","chicago":"Chu, Zonglin, Yanxiao Han, Tong Bian, Soumen De, Petr Král, and Rafal Klajn. “Supramolecular Control of Azobenzene Switching on Nanoparticles.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2019. <a href=\"https://doi.org/10.1021/jacs.8b09638\">https://doi.org/10.1021/jacs.8b09638</a>.","ista":"Chu Z, Han Y, Bian T, De S, Král P, Klajn R. 2019. Supramolecular control of azobenzene switching on nanoparticles. Journal of the American Chemical Society. 141(5), 1949–1960.","ieee":"Z. Chu, Y. Han, T. Bian, S. De, P. Král, and R. Klajn, “Supramolecular control of azobenzene switching on nanoparticles,” <i>Journal of the American Chemical Society</i>, vol. 141, no. 5. American Chemical Society, pp. 1949–1960, 2019.","short":"Z. Chu, Y. Han, T. Bian, S. De, P. Král, R. Klajn, Journal of the American Chemical Society 141 (2019) 1949–1960.","mla":"Chu, Zonglin, et al. “Supramolecular Control of Azobenzene Switching on Nanoparticles.” <i>Journal of the American Chemical Society</i>, vol. 141, no. 5, American Chemical Society, 2019, pp. 1949–60, doi:<a href=\"https://doi.org/10.1021/jacs.8b09638\">10.1021/jacs.8b09638</a>.","apa":"Chu, Z., Han, Y., Bian, T., De, S., Král, P., &#38; Klajn, R. (2019). Supramolecular control of azobenzene switching on nanoparticles. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.8b09638\">https://doi.org/10.1021/jacs.8b09638</a>"},"publisher":"American Chemical Society","intvolume":"       141","issue":"5","article_processing_charge":"No","day":"06","date_published":"2019-02-06T00:00:00Z","author":[{"first_name":"Zonglin","last_name":"Chu","full_name":"Chu, Zonglin"},{"first_name":"Yanxiao","last_name":"Han","full_name":"Han, Yanxiao"},{"full_name":"Bian, Tong","first_name":"Tong","last_name":"Bian"},{"last_name":"De","first_name":"Soumen","full_name":"De, Soumen"},{"last_name":"Král","first_name":"Petr","full_name":"Král, Petr"},{"id":"8e84690e-1e48-11ed-a02b-a1e6fb8bb53b","full_name":"Klajn, Rafal","last_name":"Klajn","first_name":"Rafal"}],"publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"title":"Supramolecular control of azobenzene switching on nanoparticles","status":"public","_id":"13373","date_created":"2023-08-01T09:39:19Z","abstract":[{"lang":"eng","text":"The reversible photoisomerization of azobenzene has been utilized to construct a plethora of systems in which optical, electronic, catalytic, and other properties can be controlled by light. However, owing to azobenzene’s hydrophobic nature, most of these examples have been realized only in organic solvents, and systems operating in water are relatively scarce. Here, we show that by coadsorbing the inherently hydrophobic azobenzenes with water-solubilizing ligands on the same nanoparticulate platforms, it is possible to render them essentially water-soluble. To this end, we developed a modified nanoparticle functionalization procedure allowing us to precisely fine-tune the amount of azobenzene on the functionalized nanoparticles. Molecular dynamics simulations helped us to identify two distinct supramolecular architectures (depending on the length of the background ligand) on these nanoparticles, which can explain their excellent aqueous solubilities. Azobenzenes adsorbed on these water-soluble nanoparticles exhibit highly reversible photoisomerization upon exposure to UV and visible light. Importantly, the mixed-monolayer approach allowed us to systematically investigate how the background ligand affects the switching properties of azobenzene. We found that the nature of the background ligand has a profound effect on the kinetics of azobenzene switching. For example, a hydroxy-terminated background ligand is capable of accelerating the back-isomerization reaction by more than 6000-fold. These results pave the way toward the development of novel light-responsive nanomaterials operating in aqueous media and, in the long run, in biological environments."}],"extern":"1","pmid":1,"year":"2019","publication_status":"published","page":"1949-1960","scopus_import":"1","oa_version":"Published Version","date_updated":"2024-10-14T12:14:23Z"},{"oa_version":"Submitted Version","date_updated":"2021-01-12T08:19:04Z","pmid":1,"year":"2019","page":"11183-11195","publication_status":"published","title":"Aromatic ring dynamics, thermal activation, and transient conformations of a 468 kDa enzyme by specific 1H–13C labeling and fast magic-angle spinning NMR","_id":"8408","status":"public","abstract":[{"text":"Aromatic residues are located at structurally important sites of many proteins. Probing their interactions and dynamics can provide important functional insight but is challenging in large proteins. Here, we introduce approaches to characterize dynamics of phenylalanine residues using 1H-detected fast magic-angle spinning (MAS) NMR combined with a tailored isotope-labeling scheme. Our approach yields isolated two-spin systems that are ideally suited for artefact-free dynamics measurements, and allows probing motions effectively without molecular-weight limitations. The application to the TET2 enzyme assembly of ~0.5 MDa size, the currently largest protein assigned by MAS NMR, provides insights into motions occurring on a wide range of time scales (ps-ms). We quantitatively probe ring flip motions, and show the temperature dependence by MAS NMR measurements down to 100 K. Interestingly, favorable line widths are observed down to 100 K, with potential implications for DNP NMR. Furthermore, we report the first 13C R1ρ MAS NMR relaxation-dispersion measurements and detect structural excursions occurring on a microsecond time scale in the entry pore to the catalytic chamber and at a trimer interface that was proposed as exit pore. We show that the labeling scheme with deuteration at ca. 50 kHz MAS provides superior resolution compared to 100 kHz MAS experiments with protonated, uniformly 13C-labeled samples.","lang":"eng"}],"date_created":"2020-09-17T10:29:00Z","extern":"1","author":[{"full_name":"Gauto, Diego F.","first_name":"Diego F.","last_name":"Gauto"},{"first_name":"Pavel","last_name":"Macek","full_name":"Macek, Pavel"},{"first_name":"Alessandro","last_name":"Barducci","full_name":"Barducci, Alessandro"},{"full_name":"Fraga, Hugo","last_name":"Fraga","first_name":"Hugo"},{"last_name":"Hessel","first_name":"Audrey","full_name":"Hessel, Audrey"},{"first_name":"Tsutomu","last_name":"Terauchi","full_name":"Terauchi, Tsutomu"},{"full_name":"Gajan, David","first_name":"David","last_name":"Gajan"},{"full_name":"Miyanoiri, Yohei","last_name":"Miyanoiri","first_name":"Yohei"},{"full_name":"Boisbouvier, Jerome","first_name":"Jerome","last_name":"Boisbouvier"},{"full_name":"Lichtenecker, Roman","first_name":"Roman","last_name":"Lichtenecker"},{"full_name":"Kainosho, Masatsune","first_name":"Masatsune","last_name":"Kainosho"},{"last_name":"Schanda","first_name":"Paul","full_name":"Schanda, Paul","orcid":"0000-0002-9350-7606","id":"7B541462-FAF6-11E9-A490-E8DFE5697425"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","language":[{"iso":"eng"}],"publication":"Journal of the American Chemical Society","keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"publisher":"American Chemical Society","citation":{"mla":"Gauto, Diego F., et al. “Aromatic Ring Dynamics, Thermal Activation, and Transient Conformations of a 468 KDa Enzyme by Specific 1H–13C Labeling and Fast Magic-Angle Spinning NMR.” <i>Journal of the American Chemical Society</i>, vol. 141, no. 28, American Chemical Society, 2019, pp. 11183–95, doi:<a href=\"https://doi.org/10.1021/jacs.9b04219\">10.1021/jacs.9b04219</a>.","apa":"Gauto, D. F., Macek, P., Barducci, A., Fraga, H., Hessel, A., Terauchi, T., … Schanda, P. (2019). Aromatic ring dynamics, thermal activation, and transient conformations of a 468 kDa enzyme by specific 1H–13C labeling and fast magic-angle spinning NMR. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.9b04219\">https://doi.org/10.1021/jacs.9b04219</a>","short":"D.F. Gauto, P. Macek, A. Barducci, H. Fraga, A. Hessel, T. Terauchi, D. Gajan, Y. Miyanoiri, J. Boisbouvier, R. Lichtenecker, M. Kainosho, P. Schanda, Journal of the American Chemical Society 141 (2019) 11183–11195.","ama":"Gauto DF, Macek P, Barducci A, et al. Aromatic ring dynamics, thermal activation, and transient conformations of a 468 kDa enzyme by specific 1H–13C labeling and fast magic-angle spinning NMR. <i>Journal of the American Chemical Society</i>. 2019;141(28):11183-11195. doi:<a href=\"https://doi.org/10.1021/jacs.9b04219\">10.1021/jacs.9b04219</a>","ieee":"D. F. Gauto <i>et al.</i>, “Aromatic ring dynamics, thermal activation, and transient conformations of a 468 kDa enzyme by specific 1H–13C labeling and fast magic-angle spinning NMR,” <i>Journal of the American Chemical Society</i>, vol. 141, no. 28. American Chemical Society, pp. 11183–11195, 2019.","chicago":"Gauto, Diego F., Pavel Macek, Alessandro Barducci, Hugo Fraga, Audrey Hessel, Tsutomu Terauchi, David Gajan, et al. “Aromatic Ring Dynamics, Thermal Activation, and Transient Conformations of a 468 KDa Enzyme by Specific 1H–13C Labeling and Fast Magic-Angle Spinning NMR.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2019. <a href=\"https://doi.org/10.1021/jacs.9b04219\">https://doi.org/10.1021/jacs.9b04219</a>.","ista":"Gauto DF, Macek P, Barducci A, Fraga H, Hessel A, Terauchi T, Gajan D, Miyanoiri Y, Boisbouvier J, Lichtenecker R, Kainosho M, Schanda P. 2019. Aromatic ring dynamics, thermal activation, and transient conformations of a 468 kDa enzyme by specific 1H–13C labeling and fast magic-angle spinning NMR. Journal of the American Chemical Society. 141(28), 11183–11195."},"issue":"28","intvolume":"       141","day":"14","date_published":"2019-06-14T00:00:00Z","article_processing_charge":"No","type":"journal_article","external_id":{"pmid":["31199882"]},"doi":"10.1021/jacs.9b04219","volume":141,"publication_identifier":{"issn":["0002-7863","1520-5126"]},"quality_controlled":"1","month":"06","article_type":"original"},{"citation":{"apa":"Rovó, P., Smith, C. A., Gauto, D., de Groot, B. L., Schanda, P., &#38; Linser, R. (2019). Mechanistic insights into microsecond time-scale motion of solid proteins using complementary 15N and 1H relaxation dispersion techniques. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.8b09258\">https://doi.org/10.1021/jacs.8b09258</a>","mla":"Rovó, Petra, et al. “Mechanistic Insights into Microsecond Time-Scale Motion of Solid Proteins Using Complementary 15N and 1H Relaxation Dispersion Techniques.” <i>Journal of the American Chemical Society</i>, vol. 141, no. 2, American Chemical Society, 2019, pp. 858–69, doi:<a href=\"https://doi.org/10.1021/jacs.8b09258\">10.1021/jacs.8b09258</a>.","ista":"Rovó P, Smith CA, Gauto D, de Groot BL, Schanda P, Linser R. 2019. Mechanistic insights into microsecond time-scale motion of solid proteins using complementary 15N and 1H relaxation dispersion techniques. Journal of the American Chemical Society. 141(2), 858–869.","ieee":"P. Rovó, C. A. Smith, D. Gauto, B. L. de Groot, P. Schanda, and R. Linser, “Mechanistic insights into microsecond time-scale motion of solid proteins using complementary 15N and 1H relaxation dispersion techniques,” <i>Journal of the American Chemical Society</i>, vol. 141, no. 2. American Chemical Society, pp. 858–869, 2019.","chicago":"Rovó, Petra, Colin A. Smith, Diego Gauto, Bert L. de Groot, Paul Schanda, and Rasmus Linser. “Mechanistic Insights into Microsecond Time-Scale Motion of Solid Proteins Using Complementary 15N and 1H Relaxation Dispersion Techniques.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2019. <a href=\"https://doi.org/10.1021/jacs.8b09258\">https://doi.org/10.1021/jacs.8b09258</a>.","ama":"Rovó P, Smith CA, Gauto D, de Groot BL, Schanda P, Linser R. Mechanistic insights into microsecond time-scale motion of solid proteins using complementary 15N and 1H relaxation dispersion techniques. <i>Journal of the American Chemical Society</i>. 2019;141(2):858-869. doi:<a href=\"https://doi.org/10.1021/jacs.8b09258\">10.1021/jacs.8b09258</a>","short":"P. Rovó, C.A. Smith, D. Gauto, B.L. de Groot, P. Schanda, R. Linser, Journal of the American Chemical Society 141 (2019) 858–869."},"publisher":"American Chemical Society","intvolume":"       141","issue":"2","article_processing_charge":"No","day":"08","date_published":"2019-01-08T00:00:00Z","author":[{"full_name":"Rovó, Petra","last_name":"Rovó","first_name":"Petra"},{"full_name":"Smith, Colin A.","last_name":"Smith","first_name":"Colin A."},{"first_name":"Diego","last_name":"Gauto","full_name":"Gauto, Diego"},{"first_name":"Bert L.","last_name":"de Groot","full_name":"de Groot, Bert L."},{"orcid":"0000-0002-9350-7606","id":"7B541462-FAF6-11E9-A490-E8DFE5697425","last_name":"Schanda","first_name":"Paul","full_name":"Schanda, Paul"},{"full_name":"Linser, Rasmus","first_name":"Rasmus","last_name":"Linser"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"publication_identifier":{"issn":["0002-7863","1520-5126"]},"month":"01","quality_controlled":"1","article_type":"original","external_id":{"pmid":["30620186"]},"type":"journal_article","volume":141,"doi":"10.1021/jacs.8b09258","pmid":1,"year":"2019","publication_status":"published","page":"858-869","oa_version":"Submitted Version","date_updated":"2021-01-12T08:19:07Z","title":"Mechanistic insights into microsecond time-scale motion of solid proteins using complementary 15N and 1H relaxation dispersion techniques","status":"public","_id":"8413","date_created":"2020-09-17T10:29:50Z","abstract":[{"lang":"eng","text":"NMR relaxation dispersion methods provide a holistic way to observe microsecond time-scale protein backbone motion both in solution and in the solid state. Different nuclei (1H and 15N) and different relaxation dispersion techniques (Bloch–McConnell and near-rotary-resonance) give complementary information about the amplitudes and time scales of the conformational dynamics and provide comprehensive insights into the mechanistic details of the structural rearrangements. In this paper, we exemplify the benefits of the combination of various solution- and solid-state relaxation dispersion methods on a microcrystalline protein (α-spectrin SH3 domain), for which we are able to identify and model the functionally relevant conformational rearrangements around the ligand recognition loop occurring on multiple microsecond time scales. The observed loop motions suggest that the SH3 domain exists in a binding-competent conformation in dynamic equilibrium with a sterically impaired ground-state conformation both in solution and in crystalline form. This inherent plasticity between the interconverting macrostates is compatible with a conformational-preselection model and provides new insights into the recognition mechanisms of SH3 domains."}],"extern":"1"},{"publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"article_type":"original","quality_controlled":"1","month":"04","type":"journal_article","external_id":{"pmid":["31017419 "],"isi":["000469292300004"]},"doi":"10.1021/jacs.9b01394","has_accepted_license":"1","volume":141,"issue":"20","intvolume":"       141","file":[{"date_created":"2019-06-25T11:59:00Z","creator":"cpetz","file_name":"JACS_April2019.pdf","file_id":"6587","file_size":6234004,"access_level":"open_access","date_updated":"2020-07-14T12:47:34Z","content_type":"application/pdf","checksum":"34d7ec837869cc6a07996b54f75696b7","relation":"main_file"}],"publisher":"American Chemical Society","citation":{"mla":"Ibáñez, Maria, et al. “Ligand-Mediated Band Engineering in Bottom-up Assembled SnTe Nanocomposites for Thermoelectric Energy Conversion.” <i>Journal of the American Chemical Society</i>, vol. 141, no. 20, American Chemical Society, 2019, pp. 8025–29, doi:<a href=\"https://doi.org/10.1021/jacs.9b01394\">10.1021/jacs.9b01394</a>.","apa":"Ibáñez, M., Hasler, R., Genç, A., Liu, Y., Kuster, B., Schuster, M., … Kovalenko, M. V. (2019). Ligand-mediated band engineering in bottom-up assembled SnTe nanocomposites for thermoelectric energy conversion. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.9b01394\">https://doi.org/10.1021/jacs.9b01394</a>","short":"M. Ibáñez, R. Hasler, A. Genç, Y. Liu, B. Kuster, M. Schuster, O. Dobrozhan, D. Cadavid, J. Arbiol, A. Cabot, M.V. Kovalenko, Journal of the American Chemical Society 141 (2019) 8025–8029.","ama":"Ibáñez M, Hasler R, Genç A, et al. Ligand-mediated band engineering in bottom-up assembled SnTe nanocomposites for thermoelectric energy conversion. <i>Journal of the American Chemical Society</i>. 2019;141(20):8025-8029. doi:<a href=\"https://doi.org/10.1021/jacs.9b01394\">10.1021/jacs.9b01394</a>","ista":"Ibáñez M, Hasler R, Genç A, Liu Y, Kuster B, Schuster M, Dobrozhan O, Cadavid D, Arbiol J, Cabot A, Kovalenko MV. 2019. Ligand-mediated band engineering in bottom-up assembled SnTe nanocomposites for thermoelectric energy conversion. Journal of the American Chemical Society. 141(20), 8025–8029.","chicago":"Ibáñez, Maria, Roger Hasler, Aziz Genç, Yu Liu, Beatrice Kuster, Maximilian Schuster, Oleksandr Dobrozhan, et al. “Ligand-Mediated Band Engineering in Bottom-up Assembled SnTe Nanocomposites for Thermoelectric Energy Conversion.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2019. <a href=\"https://doi.org/10.1021/jacs.9b01394\">https://doi.org/10.1021/jacs.9b01394</a>.","ieee":"M. Ibáñez <i>et al.</i>, “Ligand-mediated band engineering in bottom-up assembled SnTe nanocomposites for thermoelectric energy conversion,” <i>Journal of the American Chemical Society</i>, vol. 141, no. 20. American Chemical Society, pp. 8025–8029, 2019."},"date_published":"2019-04-19T00:00:00Z","day":"19","article_processing_charge":"No","file_date_updated":"2020-07-14T12:47:34Z","department":[{"_id":"MaIb"}],"ec_funded":1,"author":[{"full_name":"Ibáñez, Maria","last_name":"Ibáñez","first_name":"Maria","id":"43C61214-F248-11E8-B48F-1D18A9856A87","orcid":"0000-0001-5013-2843"},{"full_name":"Hasler, Roger","last_name":"Hasler","first_name":"Roger"},{"full_name":"Genç, Aziz","last_name":"Genç","first_name":"Aziz"},{"id":"2A70014E-F248-11E8-B48F-1D18A9856A87","orcid":"0000-0001-7313-6740","full_name":"Liu, Yu","first_name":"Yu","last_name":"Liu"},{"full_name":"Kuster, Beatrice","last_name":"Kuster","first_name":"Beatrice"},{"first_name":"Maximilian","last_name":"Schuster","full_name":"Schuster, Maximilian"},{"last_name":"Dobrozhan","first_name":"Oleksandr","full_name":"Dobrozhan, Oleksandr"},{"full_name":"Cadavid, Doris","first_name":"Doris","last_name":"Cadavid"},{"full_name":"Arbiol, Jordi","last_name":"Arbiol","first_name":"Jordi"},{"last_name":"Cabot","first_name":"Andreu","full_name":"Cabot, Andreu"},{"full_name":"Kovalenko, Maksym V.","first_name":"Maksym V.","last_name":"Kovalenko"}],"language":[{"iso":"eng"}],"publication":"Journal of the American Chemical Society","ddc":["540"],"user_id":"c635000d-4b10-11ee-a964-aac5a93f6ac1","_id":"6586","status":"public","title":"Ligand-mediated band engineering in bottom-up assembled SnTe nanocomposites for thermoelectric energy conversion","abstract":[{"text":"The bottom-up assembly of colloidal nanocrystals is a versatile methodology to produce composite nanomaterials with precisely tuned electronic properties. Beyond the synthetic control over crystal domain size, shape, crystal phase, and composition, solution-processed nanocrystals allow exquisite surface engineering. This provides additional means to modulate the nanomaterial characteristics and particularly its electronic transport properties. For instance, inorganic surface ligands can be used to tune the type and concentration of majority carriers or to modify the electronic band structure. Herein, we report the thermoelectric properties of SnTe nanocomposites obtained from the consolidation of surface-engineered SnTe nanocrystals into macroscopic pellets. A CdSe-based ligand is selected to (i) converge the light and heavy bands through partial Cd alloying and (ii) generate CdSe nanoinclusions as a secondary phase within the SnTe matrix, thereby reducing the thermal conductivity. These SnTe-CdSe nanocomposites possess thermoelectric figures of merit of up to 1.3 at 850 K, which is, to the best of our knowledge, the highest thermoelectric figure of merit reported for solution-processed SnTe.","lang":"eng"}],"oa":1,"date_created":"2019-06-25T11:53:35Z","isi":1,"year":"2019","pmid":1,"project":[{"name":"ISTplus - Postdoctoral Fellowships","grant_number":"754411","call_identifier":"H2020","_id":"260C2330-B435-11E9-9278-68D0E5697425"}],"publication_status":"published","page":"8025-8029","oa_version":"Published Version","scopus_import":"1","date_updated":"2025-04-14T07:44:06Z"},{"year":"2019","pmid":1,"OA_type":"closed access","publication_status":"published","page":"15471-15476","scopus_import":"1","oa_version":"None","date_updated":"2024-12-10T12:39:27Z","_id":"17918","status":"public","title":"Permethylation introduces destructive quantum interference in saturated silanes","extern":"1","date_created":"2024-09-09T07:42:26Z","abstract":[{"lang":"eng","text":"The single-molecule conductance of silanes is suppressed due to destructive quantum interference in conformations with cisoid dihedral angles along the molecular backbone. Yet, despite the structural similarity, σ-interference effects have not been observed in alkanes. Here we report that the methyl substituents used in silanes are a prerequisite for σ-interference in these systems. Through density functional theory calculations, we find that the destructive interference is not evident to the same extent in nonmethylated silanes. We find the same is true in alkanes as the transmission is significantly suppressed in permethylated cyclic and bicyclic alkanes. Using scanning tunneling microscope break-junction method we determine the single-molecule conductance of functionalized cyclohexane and bicyclo[2.2.2]octane that are found to be higher than that of equivalent permethylated silanes. Rather than the difference between carbon and silicon atoms in the molecular backbones, our calculations reveal that it is primarily the difference between hydrogen and methyl substituents that result in the different electron transport properties of nonmethylated alkanes and permethylated silanes. Chemical substituents play an important role in determining the single-molecule conductance of saturated molecules, and this must be considered when we improve and expand the chemical design of insulating organic molecules."}],"intvolume":"       141","issue":"39","citation":{"ama":"Garner MH, Li H, Neupane M, et al. Permethylation introduces destructive quantum interference in saturated silanes. <i>Journal of the American Chemical Society</i>. 2019;141(39):15471-15476. doi:<a href=\"https://doi.org/10.1021/jacs.9b06965\">10.1021/jacs.9b06965</a>","ieee":"M. H. Garner <i>et al.</i>, “Permethylation introduces destructive quantum interference in saturated silanes,” <i>Journal of the American Chemical Society</i>, vol. 141, no. 39. American Chemical Society, pp. 15471–15476, 2019.","ista":"Garner MH, Li H, Neupane M, Zou Q, Liu T, Su TA, Shangguan Z, Paley DW, Ng F, Xiao S, Nuckolls C, Venkataraman L, Solomon GC. 2019. Permethylation introduces destructive quantum interference in saturated silanes. Journal of the American Chemical Society. 141(39), 15471–15476.","chicago":"Garner, Marc H., Haixing Li, Madhav Neupane, Qi Zou, Taifeng Liu, Timothy A. Su, Zhichun Shangguan, et al. “Permethylation Introduces Destructive Quantum Interference in Saturated Silanes.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2019. <a href=\"https://doi.org/10.1021/jacs.9b06965\">https://doi.org/10.1021/jacs.9b06965</a>.","short":"M.H. Garner, H. Li, M. Neupane, Q. Zou, T. Liu, T.A. Su, Z. Shangguan, D.W. Paley, F. Ng, S. Xiao, C. Nuckolls, L. Venkataraman, G.C. Solomon, Journal of the American Chemical Society 141 (2019) 15471–15476.","mla":"Garner, Marc H., et al. “Permethylation Introduces Destructive Quantum Interference in Saturated Silanes.” <i>Journal of the American Chemical Society</i>, vol. 141, no. 39, American Chemical Society, 2019, pp. 15471–76, doi:<a href=\"https://doi.org/10.1021/jacs.9b06965\">10.1021/jacs.9b06965</a>.","apa":"Garner, M. H., Li, H., Neupane, M., Zou, Q., Liu, T., Su, T. A., … Solomon, G. C. (2019). Permethylation introduces destructive quantum interference in saturated silanes. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.9b06965\">https://doi.org/10.1021/jacs.9b06965</a>"},"publisher":"American Chemical Society","article_processing_charge":"No","date_published":"2019-09-10T00:00:00Z","day":"10","author":[{"full_name":"Garner, Marc H.","last_name":"Garner","first_name":"Marc H."},{"first_name":"Haixing","last_name":"Li","full_name":"Li, Haixing"},{"first_name":"Madhav","last_name":"Neupane","full_name":"Neupane, Madhav"},{"last_name":"Zou","first_name":"Qi","full_name":"Zou, Qi"},{"full_name":"Liu, Taifeng","last_name":"Liu","first_name":"Taifeng"},{"first_name":"Timothy A.","last_name":"Su","full_name":"Su, Timothy A."},{"full_name":"Shangguan, Zhichun","last_name":"Shangguan","first_name":"Zhichun"},{"full_name":"Paley, Daniel W.","last_name":"Paley","first_name":"Daniel W."},{"last_name":"Ng","first_name":"Fay","full_name":"Ng, Fay"},{"last_name":"Xiao","first_name":"Shengxiong","full_name":"Xiao, Shengxiong"},{"first_name":"Colin","last_name":"Nuckolls","full_name":"Nuckolls, Colin"},{"full_name":"Venkataraman, Latha","first_name":"Latha","last_name":"Venkataraman","id":"9ebb78a5-cc0d-11ee-8322-fae086a32caf","orcid":"0000-0002-6957-6089"},{"first_name":"Gemma C.","last_name":"Solomon","full_name":"Solomon, Gemma C."}],"language":[{"iso":"eng"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication":"Journal of the American Chemical Society","publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"article_type":"original","month":"09","quality_controlled":"1","external_id":{"pmid":["31500410"]},"type":"journal_article","volume":141,"doi":"10.1021/jacs.9b06965"},{"publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"article_type":"original","month":"08","quality_controlled":"1","external_id":{"pmid":["30074782"]},"type":"journal_article","volume":140,"doi":"10.1021/jacs.8b06067","intvolume":"       140","issue":"33","citation":{"chicago":"Hemmer, James R., Zachariah A. Page, Kyle D. Clark, Friedrich J Stricker, Neil D. Dolinski, Craig J. Hawker, and Javier Read de Alaniz. “Controlling Dark Equilibria and Enhancing Donor–Acceptor Stenhouse Adduct Photoswitching Properties through Carbon Acid Design.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2018. <a href=\"https://doi.org/10.1021/jacs.8b06067\">https://doi.org/10.1021/jacs.8b06067</a>.","ieee":"J. R. Hemmer <i>et al.</i>, “Controlling dark equilibria and enhancing donor–acceptor Stenhouse adduct photoswitching properties through carbon acid design,” <i>Journal of the American Chemical Society</i>, vol. 140, no. 33. American Chemical Society, pp. 10425–10429, 2018.","ista":"Hemmer JR, Page ZA, Clark KD, Stricker FJ, Dolinski ND, Hawker CJ, Read de Alaniz J. 2018. Controlling dark equilibria and enhancing donor–acceptor Stenhouse adduct photoswitching properties through carbon acid design. Journal of the American Chemical Society. 140(33), 10425–10429.","ama":"Hemmer JR, Page ZA, Clark KD, et al. Controlling dark equilibria and enhancing donor–acceptor Stenhouse adduct photoswitching properties through carbon acid design. <i>Journal of the American Chemical Society</i>. 2018;140(33):10425-10429. doi:<a href=\"https://doi.org/10.1021/jacs.8b06067\">10.1021/jacs.8b06067</a>","short":"J.R. Hemmer, Z.A. Page, K.D. Clark, F.J. Stricker, N.D. Dolinski, C.J. Hawker, J. Read de Alaniz, Journal of the American Chemical Society 140 (2018) 10425–10429.","apa":"Hemmer, J. R., Page, Z. A., Clark, K. D., Stricker, F. J., Dolinski, N. D., Hawker, C. J., &#38; Read de Alaniz, J. (2018). Controlling dark equilibria and enhancing donor–acceptor Stenhouse adduct photoswitching properties through carbon acid design. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.8b06067\">https://doi.org/10.1021/jacs.8b06067</a>","mla":"Hemmer, James R., et al. “Controlling Dark Equilibria and Enhancing Donor–Acceptor Stenhouse Adduct Photoswitching Properties through Carbon Acid Design.” <i>Journal of the American Chemical Society</i>, vol. 140, no. 33, American Chemical Society, 2018, pp. 10425–29, doi:<a href=\"https://doi.org/10.1021/jacs.8b06067\">10.1021/jacs.8b06067</a>."},"publisher":"American Chemical Society","article_processing_charge":"No","day":"03","date_published":"2018-08-03T00:00:00Z","author":[{"full_name":"Hemmer, James R.","last_name":"Hemmer","first_name":"James R."},{"full_name":"Page, Zachariah A.","first_name":"Zachariah A.","last_name":"Page"},{"first_name":"Kyle D.","last_name":"Clark","full_name":"Clark, Kyle D."},{"first_name":"Friedrich J","last_name":"Stricker","full_name":"Stricker, Friedrich J","id":"7aca2cfc-46cf-11f0-abd3-8c96b5186745"},{"first_name":"Neil D.","last_name":"Dolinski","full_name":"Dolinski, Neil D."},{"first_name":"Craig J.","last_name":"Hawker","full_name":"Hawker, Craig J."},{"first_name":"Javier","last_name":"Read de Alaniz","full_name":"Read de Alaniz, Javier"}],"publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"ddc":["540"],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","_id":"21822","status":"public","title":"Controlling dark equilibria and enhancing donor–acceptor Stenhouse adduct photoswitching properties through carbon acid design","extern":"1","date_created":"2026-05-06T10:58:29Z","abstract":[{"text":"A novel library of tunable negative photochromic compounds, donor–acceptor Stenhouse adducts (DASAs), is reported. Tailoring the electron deficient “acceptor” moiety yielded DASAs that can be activated with mild visible and far red light. The effect of acceptor composition on reactivity, absorption, equilibrium, and cyclability is exploited for the design of high performance photoswitches. The structural changes to the carbon acid acceptor also provide access to new, more structurally diverse DASA derivatives by facilitating the ring-opening reaction with electron deficient amine donors.","lang":"eng"}],"year":"2018","pmid":1,"OA_type":"closed access","publication_status":"published","page":"10425-10429","oa_version":"None","scopus_import":"1","date_updated":"2026-05-11T08:46:52Z"},{"doi":"10.1021/jacs.8b10296","volume":140,"type":"journal_article","external_id":{"pmid":["30372051"]},"article_type":"original","quality_controlled":"1","month":"10","publication_identifier":{"issn":["0002-7863"],"eissn":["1520-5126"]},"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication":"Journal of the American Chemical Society","language":[{"iso":"eng"}],"author":[{"full_name":"Li, Haixing","last_name":"Li","first_name":"Haixing"},{"full_name":"Garner, Marc H.","first_name":"Marc H.","last_name":"Garner"},{"full_name":"Shangguan, Zhichun","first_name":"Zhichun","last_name":"Shangguan"},{"first_name":"Yan","last_name":"Chen","full_name":"Chen, Yan"},{"last_name":"Zheng","first_name":"Qianwen","full_name":"Zheng, Qianwen"},{"full_name":"Su, Timothy A.","first_name":"Timothy A.","last_name":"Su"},{"first_name":"Madhav","last_name":"Neupane","full_name":"Neupane, Madhav"},{"full_name":"Liu, Taifeng","last_name":"Liu","first_name":"Taifeng"},{"last_name":"Steigerwald","first_name":"Michael L.","full_name":"Steigerwald, Michael L."},{"full_name":"Ng, Fay","last_name":"Ng","first_name":"Fay"},{"first_name":"Colin","last_name":"Nuckolls","full_name":"Nuckolls, Colin"},{"full_name":"Xiao, Shengxiong","first_name":"Shengxiong","last_name":"Xiao"},{"last_name":"Solomon","first_name":"Gemma C.","full_name":"Solomon, Gemma C."},{"first_name":"Latha","last_name":"Venkataraman","full_name":"Venkataraman, Latha","orcid":"0000-0002-6957-6089","id":"9ebb78a5-cc0d-11ee-8322-fae086a32caf"}],"day":"17","date_published":"2018-10-17T00:00:00Z","article_processing_charge":"No","issue":"44","intvolume":"       140","publisher":"American Chemical Society","citation":{"ama":"Li H, Garner MH, Shangguan Z, et al. Large variations in the single-molecule conductance of cyclic and bicyclic silanes. <i>Journal of the American Chemical Society</i>. 2018;140(44):15080-15088. doi:<a href=\"https://doi.org/10.1021/jacs.8b10296\">10.1021/jacs.8b10296</a>","ista":"Li H, Garner MH, Shangguan Z, Chen Y, Zheng Q, Su TA, Neupane M, Liu T, Steigerwald ML, Ng F, Nuckolls C, Xiao S, Solomon GC, Venkataraman L. 2018. Large variations in the single-molecule conductance of cyclic and bicyclic silanes. Journal of the American Chemical Society. 140(44), 15080–15088.","chicago":"Li, Haixing, Marc H. Garner, Zhichun Shangguan, Yan Chen, Qianwen Zheng, Timothy A. Su, Madhav Neupane, et al. “Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2018. <a href=\"https://doi.org/10.1021/jacs.8b10296\">https://doi.org/10.1021/jacs.8b10296</a>.","ieee":"H. Li <i>et al.</i>, “Large variations in the single-molecule conductance of cyclic and bicyclic silanes,” <i>Journal of the American Chemical Society</i>, vol. 140, no. 44. American Chemical Society, pp. 15080–15088, 2018.","short":"H. Li, M.H. Garner, Z. Shangguan, Y. Chen, Q. Zheng, T.A. Su, M. Neupane, T. Liu, M.L. Steigerwald, F. Ng, C. Nuckolls, S. Xiao, G.C. Solomon, L. Venkataraman, Journal of the American Chemical Society 140 (2018) 15080–15088.","mla":"Li, Haixing, et al. “Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes.” <i>Journal of the American Chemical Society</i>, vol. 140, no. 44, American Chemical Society, 2018, pp. 15080–88, doi:<a href=\"https://doi.org/10.1021/jacs.8b10296\">10.1021/jacs.8b10296</a>.","apa":"Li, H., Garner, M. H., Shangguan, Z., Chen, Y., Zheng, Q., Su, T. A., … Venkataraman, L. (2018). Large variations in the single-molecule conductance of cyclic and bicyclic silanes. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.8b10296\">https://doi.org/10.1021/jacs.8b10296</a>"},"extern":"1","abstract":[{"text":"Linear silanes are efficient molecular wires due to strong σ-conjugation in the transoid conformation; however, the structure–function relationship for the conformational dependence of the single-molecule conductance of silanes remains untested. Here we report the syntheses, electrical measurements, and theoretical characterization of four series of functionalized cyclic and bicyclic silanes including a cyclotetrasilane, a cyclopentasilane, a bicyclo[2.2.1]heptasilane, and a bicyclo[2.2.2]octasilane, which are all extended by linear silicon linkers of varying length. We find an unusual variation of the single-molecule conductance among the four series at each linker length. We determine the relative conductance of the (bi)cyclic silicon structures by using the common length dependence of the four series rather than comparing the conductance at a single length. In contrast with the cyclic π-conjugated molecules, the conductance of σ-conjugated (bi)cyclic silanes is dominated by a single path through the molecule and is controlled by the dihedral angles along this path. This strong sensitivity to molecular conformation dictates the single-molecule conductance of σ-conjugated silanes and allows for systematic control of the conductance through molecular design.","lang":"eng"}],"date_created":"2024-09-09T07:53:50Z","status":"public","_id":"17927","title":"Large variations in the single-molecule conductance of cyclic and bicyclic silanes","date_updated":"2024-12-11T08:21:09Z","oa_version":"None","scopus_import":"1","publication_status":"published","page":"15080-15088","OA_type":"closed access","year":"2018","pmid":1}]