---
res:
  bibo_abstract:
  - Molecular electrocatalysis is commonly interpreted through electronic descriptors,
    implicitly treating catalysts as mechanically passive during redox cycling. Yet,
    electron transfer often imposes structural demands on molecular scaffolds, raising
    the question of whether internal mechanical constraints can directly regulate
    access to reactive states and, in turn, catalytic outcomes. Addressing this question
    has remained challenging because mechanical effects are typically inseparable
    from changes in composition or electronic structure. Here, we achieve this separation
    by exploiting two constitutionally identical molecular catalysts whose only distinction
    is ligand geometry. This minimal geometric variation enables or suppresses intramolecular
    hydrogen bonding, thereby encoding distinct mechanical constraints that isolate
    molecular mechanics as a variable in redox accessibility. In the α isomer, molecular
    constraints impose a mechanically enforced barrier that severely limits access
    to the reactive redox state. This disrupts the temporal ordering of elementary
    steps, and diverts reactivity toward competing hydrogen evolution, eroding both
    selectivity and stability. In contrast, mechanical compliance in the β isomer
    enables facile access to the redox-active state, allowing CO2 activation to intrinsically
    outpace water activation and yielding CO selectivities exceeding 92%. Operando
    spectroscopy and real-time mass spectrometry, combined with computational simulation,
    directly resolve this mechanically gated reaction sequence as it unfolds. Molecular
    mechanics thus emerge as determinants that link electron flow to reaction sequencing
    and catalytic selectivity, revealing that constitutionally similar catalysts can
    be mechanically, and therefore catalytically, distinct.@eng
  bibo_authorlist:
  - foaf_Person:
      foaf_givenName: Rahul Mahadeo
      foaf_name: Mendhe, Rahul Mahadeo
      foaf_surname: Mendhe
  - foaf_Person:
      foaf_givenName: Neethu
      foaf_name: Christudas Dargily, Neethu
      foaf_surname: Christudas Dargily
      foaf_workInfoHomepage: http://www.librecat.org/personId=19edef5c-384c-11ef-8188-c73c9c31d601
  - foaf_Person:
      foaf_givenName: Alagar Raja
      foaf_name: Kottaichamy, Alagar Raja
      foaf_surname: Kottaichamy
  - foaf_Person:
      foaf_givenName: Shifali
      foaf_name: Dutt, Shifali
      foaf_surname: Dutt
  - foaf_Person:
      foaf_givenName: Mukaddar
      foaf_name: Sk, Mukaddar
      foaf_surname: Sk
  - foaf_Person:
      foaf_givenName: Harish
      foaf_name: Makri Nimbegondi Kotresh, Harish
      foaf_surname: Makri Nimbegondi Kotresh
  - foaf_Person:
      foaf_givenName: Musthafa
      foaf_name: Ottakam Thotiyl, Musthafa
      foaf_surname: Ottakam Thotiyl
  bibo_doi: 10.1021/jacs.6c02632
  dct_date: 2026^xs_gYear
  dct_isPartOf:
  - http://id.crossref.org/issn/0002-7863
  - http://id.crossref.org/issn/1520-5126
  dct_language: eng
  dct_publisher: American Chemical Society@
  dct_title: Mechanical gating of redox access in molecular electrocatalysis@
  fabio_hasPubmedId: '42319128'
...