---
res:
  bibo_abstract:
  - "In nature, light is harvested by photoactive proteins to drive a range of biological
    processes, including photosynthesis, phototaxis, vision, and ultimately life.
    Bacteriorhodopsin, for example, is a protein embedded within archaeal cell membranes
    that binds the chromophore retinal within its hydrophobic pocket. Exposure to
    light triggers regioselective photoisomerization of the confined retinal, which
    in turn initiates a cascade of conformational changes within the protein, triggering
    proton flux against the concentration gradient, providing the microorganisms with
    the energy to live. We are inspired by these functions in nature to harness light
    energy using synthetic photoswitches under confinement. Like retinal, synthetic
    photoswitches require some degree of conformational flexibility to isomerize.
    In nature, the conformational change associated with retinal isomerization is
    accommodated by the structural flexibility of the opsin host, yet it results in
    steric communication between the chromophore and the protein. Similarly, we strive
    to design systems wherein isomerization of confined photoswitches results in steric
    communication between a photoswitch and its confining environment. To achieve
    this aim, a balance must be struck between molecular crowding and conformational
    freedom under confinement: too much crowding prevents switching, whereas too much
    freedom resembles switching of isolated molecules in solution, preventing communication.\r\n\r\nIn
    this Account, we discuss five classes of synthetic light-switchable compounds—diarylethenes,
    anthracenes, azobenzenes, spiropyrans, and donor–acceptor Stenhouse adducts—comparing
    their behaviors under confinement and in solution. The environments employed to
    confine these photoswitches are diverse, ranging from planar surfaces to nanosized
    cavities within coordination cages, nanoporous frameworks, and nanoparticle aggregates.
    The trends that emerge are primarily dependent on the nature of the photoswitch
    and not on the material used for confinement. In general, we find that photoswitches
    requiring less conformational freedom for switching are, as expected, more straightforward
    to isomerize reversibly under confinement. Because these compounds undergo only
    small structural changes upon isomerization, however, switching does not propagate
    into communication with their environment. Conversely, photoswitches that require
    more conformational freedom are more challenging to switch under confinement but
    also can influence system-wide behavior.\r\n\r\nAlthough we are primarily interested
    in the effects of geometric constraints on photoswitching under confinement, additional
    effects inevitably emerge when a compound is removed from solution and placed
    within a new, more crowded environment. For instance, we have found that compounds
    that convert to zwitterionic isomers upon light irradiation often experience stabilization
    of these forms under confinement. This effect results from the mutual stabilization
    of zwitterions that are brought into close proximity on surfaces or within cavities.
    Furthermore, photoswitches can experience preorganization under confinement, influencing
    the selectivity and efficiency of their photoreactions. Because intermolecular
    interactions arising from confinement cannot be considered independently from
    the effects of geometric constraints, we describe all confinement effects concurrently
    throughout this Account.@eng"
  bibo_authorlist:
  - foaf_Person:
      foaf_givenName: Angela B.
      foaf_name: Grommet, Angela B.
      foaf_surname: Grommet
  - foaf_Person:
      foaf_givenName: Lucia M.
      foaf_name: Lee, Lucia M.
      foaf_surname: Lee
  - foaf_Person:
      foaf_givenName: Rafal
      foaf_name: Klajn, Rafal
      foaf_surname: Klajn
      foaf_workInfoHomepage: http://www.librecat.org/personId=8e84690e-1e48-11ed-a02b-a1e6fb8bb53b
  bibo_doi: 10.1021/acs.accounts.0c00434
  bibo_issue: '11'
  bibo_volume: 53
  dct_date: 2020^xs_gYear
  dct_isPartOf:
  - http://id.crossref.org/issn/0001-4842
  - http://id.crossref.org/issn/1520-4898
  dct_language: eng
  dct_publisher: American Chemical Society@
  dct_subject:
  - General Medicine
  - General Chemistry
  dct_title: Molecular photoswitching in confined spaces@
  fabio_hasPubmedId: '32969638'
...