{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T16:25:38Z","timestamp":1788279938119,"version":"build-2803163510"},"reference-count":94,"publisher":"Wiley","issue":"49","license":[{"start":{"date-parts":[[2026,6,5]],"date-time":"2026-06-05T00:00:00Z","timestamp":1780617600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,6,5]],"date-time":"2026-06-05T00:00:00Z","timestamp":1780617600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Small"],"published-print":{"date-parts":[[2026,9]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    As atomic\u2010scale archetypes for multi\u2010electron transfer, iron\u2013sulfur clusters are compelling candidates for the design of redox\u2010active, catalytic nanomaterials; yet, translating their enzymatic proficiency into robust synthetic platforms remains a challenge. A key bottleneck lies in replicating the outer\u2010sphere environment, which modulates the cluster's electronic landscape, provides site\u2010isolation, and facilitates catalytic pathways via programmable noncovalent interactions. Herein, we demonstrate a host\u2010guest strategy for systematically tuning iron\u2013sulfur cofactor models within tetrahedral\n                    <jats:bold>\n                      [M\n                      <jats:sub>4<\/jats:sub>\n                      L\n                      <jats:sub>6<\/jats:sub>\n                      ]\n                      <jats:sup>8+<\/jats:sup>\n                    <\/jats:bold>\n                    cages (M = Ni, Fe, Zn). Successful encapsulation of [Fe\n                    <jats:sub>4<\/jats:sub>\n                    S\n                    <jats:sub>4<\/jats:sub>\n                    (SR)\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sup>2\u2212<\/jats:sup>\n                    (R = Ph, \u2500CH\n                    <jats:sub>2<\/jats:sub>\n                    CH\n                    <jats:sub>2<\/jats:sub>\n                    OH) was confirmed by 1D\/2D NMR spectroscopy and ESI mass spectrometry, while titration studies confirmed association constants (\n                    <jats:italic>K<\/jats:italic>\n                    <jats:sub>a<\/jats:sub>\n                    ) &gt; 10\n                    <jats:sup>7<\/jats:sup>\n                    <jats:sc>m<\/jats:sc>\n                    <jats:sup>\u22121<\/jats:sup>\n                    . Spectroscopic characterization by\n                    <jats:sup>57<\/jats:sup>\n                    Fe M\u00f6ssbauer, X\u2010ray photoelectron, IR, and UV\u2013vis spectroscopy reveals significant shifts in Fe\u2500S bond covalency and electron density that converge toward those of the native, protein\u2010bound cofactors. Control studies with [Fe\n                    <jats:sub>4<\/jats:sub>\n                    S\n                    <jats:sub>4<\/jats:sub>\n                    (S\n                    <jats:italic>\n                      <jats:sup>t<\/jats:sup>\n                    <\/jats:italic>\n                    Bu)\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sup>2\u2212<\/jats:sup>\n                    , which associates with the host primarily through outer\u2010sphere ion pairing, demonstrate that while the electrostatic field generated by the framework's corner vertices is a primary driver of these electronic perturbations, internal confinement effects such as\n                    <jats:italic>\u03c0\u2013\u03c0<\/jats:italic>\n                    stacking and hydrogen bonding provide important secondary modulations. This work establishes a foundation for utilizing cage\u2010stabilized cofactors in the development of sophisticated, energy\u2010efficient catalytic systems.\n                  <\/jats:p>","DOI":"10.1002\/smll.74001","type":"journal-article","created":{"date-parts":[[2026,6,5]],"date-time":"2026-06-05T10:44:34Z","timestamp":1780656274000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Outer\u2010Sphere Tuning of Synthetic Iron\u2013Sulfur Clusters Within Nanoscale Cage Frameworks"],"prefix":"10.1002","volume":"22","author":[{"given":"Rupal","family":"Baliyan","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Minnesota  Twin Cities Minnesota USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shelby T.","family":"Davis","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Minnesota  Twin Cities Minnesota USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jan\u2010Niklas","family":"Boyn","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Minnesota  Twin Cities Minnesota USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6636-4128","authenticated-orcid":false,"given":"Gwendolyn A.","family":"Bailey","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Minnesota  Twin Cities Minnesota 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