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S. Department of Energy, Office of Science, Basic Energy Sciences","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,7,29]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Typical Cu(II\/I) complexes exhibit hallmark structural changes during their electron transfer (ET) reactions that result from the (pseudo) Jahn-Teller distortions and changes in polarizability inherent to their d9\/d10 configurations. Given that such structural changes incur large reorganization energy penalties, the slow rates of ET characteristic of these compounds are unsuprising. However, we recently reported a set of Cu(II\/I) complexes that undergo significant and well-defined structural changes during their redox reactions yet exhibit rapid (&amp;gt;105 M\u20131 s\u20131) ET self-exchange rate constants (k11). To explain these results, we proposed a pre-equilibrium model in which inherent conformational fluxionality in one of the two oxidation states provides access to pathways involving lower reorganization energies during the ET event. Herein, we report our results testing this hypothesis through the preparation and study of a homologous series of compounds exhibiting varying extents of conformational fluxionality in the Cu(I) state. We characterize these compounds electrochemically, structurally, and by variable temperature NMR spectroscopy to provide experimental evidence for increased fluxionality across the series. We then correlate the trend with increasing k11 through NMR linewidth broadening experiments, further taking care to define the impacts of solvent impurities therein. Finally, the nature of the conformational rearrangements and their relation to increased k11 are explored computationally to reveal differential Boltzmann populations of conformers across the series. The cumulative results of these studies support a previously underappreciated strategy for overcoming barriers to slow ET kinetics: namely through the incorporation of conformational fluxionality.<\/jats:p>","DOI":"10.1021\/jacs.6c10562","type":"journal-article","created":{"date-parts":[[2026,7,18]],"date-time":"2026-07-18T13:26:14Z","timestamp":1784381174000},"page":"31498-31509","source":"Crossref","is-referenced-by-count":1,"title":["Assessing the Impacts\nof Conformational Fluxionality\non Copper(II\/I) Electron Transfer Self-Exchange"],"prefix":"10.1021","volume":"148","author":[{"given":"Aditi","family":"Singh","sequence":"first","affiliation":[{"name":"University of Illinois, Urbana\u2212Champaign , , , ,","place":["Urbana, Illinois, United States, 61801"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-3291-3014","authenticated-orcid":true,"given":"Emmanuel Adu","family":"Fosu","sequence":"additional","affiliation":[{"name":"North Carolina State University , , , ,","place":["Raleigh, North Carolina, United States, 27695"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-0397-6378","authenticated-orcid":true,"given":"Shuohao","family":"Wang","sequence":"additional","affiliation":[{"name":"University of Illinois, Urbana\u2212Champaign , , , ,","place":["Urbana, Illinois, United States, 61801"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7124-8300","authenticated-orcid":true,"given":"Elena","family":"Jakubikova","sequence":"additional","affiliation":[{"name":"North Carolina State University , , , ,","place":["Raleigh, North Carolina, United States, 27695"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1076-9318","authenticated-orcid":true,"given":"Lisa","family":"Olshansky","sequence":"additional","affiliation":[{"name":"University of Illinois, Urbana\u2212Champaign , , , ,","place":["Urbana, Illinois, United States, 61801"]},{"name":"University of Illinois at Urbana\u2212Champaign , , , ,","place":["Urbana, Illinois, United States, 61801"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,18]]},"reference":[{"key":"2026073109202612600_cit1","doi-asserted-by":"publisher","first-page":"651","DOI":"10.1021\/cr020630e","article-title":"Electron\nTransfer by Copper Centers","volume":"104","author":"Rorabacher","year":"2004","journal-title":"Chem. 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Chem."},{"key":"2026073109202612600_cit4","doi-asserted-by":"publisher","first-page":"8274","DOI":"10.1039\/D2SC02910C","article-title":"Manipulating Electron Transfer \u2013 the Influence\nof Substituents on Novel Copper Guanidine Quinolinyl Complexes","volume":"13","author":"Heck","year":"2022","journal-title":"Chem. Sci."},{"key":"2026073109202612600_cit5","doi-asserted-by":"publisher","first-page":"458","DOI":"10.1021\/ic061501+","article-title":"Stability\nConstants: A New Twist in Transition Metal Bispidine Chemistry","volume":"46","author":"Born","year":"2007","journal-title":"Inorg. Chem."},{"key":"2026073109202612600_cit6","doi-asserted-by":"publisher","first-page":"12","DOI":"10.1021\/ic980926w","article-title":"Internal Reorganization\nEnergies for Copper Redox Couples: The Slow Electron-Transfer Reactions\nof the [CuII\/I(Bib)2]2+\/+ Couple","volume":"38","author":"Xie","year":"1999","journal-title":"Inorg. 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Comparison of NMR Self-Exchange Relaxation and\nReduction and Oxidation Cross-Reaction Kinetics for a Macrocyclic\nAmino Tetrathiaether-Copper(II\/I) Complex in Aqueous Solution","volume":"32","author":"Vande Linde","year":"1993","journal-title":"Inorg. Chem."},{"key":"2026073109202612600_cit27","doi-asserted-by":"publisher","first-page":"4322","DOI":"10.1021\/ic990365o","article-title":"A Structural Strategy for Generating Rapid Electron-Transfer\nKinetics in Copper(II\/I) Systems","volume":"38","author":"Krylova","year":"1999","journal-title":"Inorg. Chem."},{"key":"2026073109202612600_cit28","doi-asserted-by":"publisher","first-page":"5217","DOI":"10.1021\/ja068960u","article-title":"A Definitive\nExample of a Geometric \u201cEntatic State\u201d Effect: Electron-Transfer\nKinetics for a Copper(II\/I) Complex Involving A Quinquedentate Macrocyclic\nTrithiaether\u2013Bipyridine Ligand","volume":"129","author":"Chaka","year":"2007","journal-title":"J. Am.\nChem. Soc."},{"key":"2026073109202612600_cit29","doi-asserted-by":"publisher","first-page":"3101","DOI":"10.1002\/anie.201511527","article-title":"Hydrogen Bonds Dictate\nthe Coordination Geometry of\nCopper: Characterization of a Square-Planar Copper(I) Complex","volume":"55","author":"Dahl","year":"2016","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026073109202612600_cit30","doi-asserted-by":"publisher","first-page":"3684","DOI":"10.1039\/D4CC06406B","article-title":"The Golden Goal of Entatic State Model Design: Lowering\nthe Internal Reorganization Energy Leads to Exponential Increase in\nElectron Transfer Rate","volume":"61","author":"Seitz","year":"2025","journal-title":"Chem. Commun."},{"key":"2026073109202612600_cit31","doi-asserted-by":"publisher","first-page":"3878","DOI":"10.1021\/ja809834k","article-title":"Three-Coordinate\nCopper(I) Amido and Aminyl Radical Complexes","volume":"131","author":"Mankad","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"2026073109202612600_cit32","doi-asserted-by":"publisher","first-page":"6212","DOI":"10.1039\/D2DT00312K","article-title":"Conformationally\nDynamic Copper Coordination Complexes","volume":"51","author":"Charette","year":"2022","journal-title":"Dalton\nTrans."},{"key":"2026073109202612600_cit33","doi-asserted-by":"publisher","first-page":"12116","DOI":"10.1021\/jacs.2c02580","article-title":"Toward Improved\nCharge Separation through Conformational Control in Copper Coordination\nComplexes","volume":"144","author":"Griffin","year":"2022","journal-title":"J. Am. Chem. Soc."},{"key":"2026073109202612600_cit34","doi-asserted-by":"publisher","first-page":"7747","DOI":"10.1021\/acs.jpca.3c04269","article-title":"Excited State\nDynamics of a Conformationally Fluxional Copper Coordination Complex","volume":"127","author":"Charette","year":"2023","journal-title":"J. Phys. Chem. 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Phys."},{"key":"2026073109202612600_cit38","volume-title":"Dynamic NMR\nSpectroscopy","author":"Sandstro\u0308m","year":"1982"},{"key":"2026073109202612600_cit39","doi-asserted-by":"publisher","first-page":"10411","DOI":"10.1021\/ja00052a042","article-title":"Gated Electron-Transfer Behavior in Copper(II\/I) Systems.\nComparison of the Kinetics for Homogeneous Cross Reactions, NMR Self-Exchange\nRelaxation, and Electrochemical Data for a Copper Macrocyclic Tetrathioether\nComplex in Aqueous Solution","volume":"114","author":"Meagher","year":"1992","journal-title":"J. Am. Chem. Soc."},{"key":"2026073109202612600_cit40","doi-asserted-by":"publisher","first-page":"3","DOI":"10.1107\/S2053273314026370","article-title":"It SHELXT\n\u2013 Integrated Space-Group and Crystal-Structure Determination","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr., Sect. 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Educ."},{"key":"2026073109202612600_cit51","doi-asserted-by":"publisher","first-page":"329","DOI":"10.1021\/ed084p329","article-title":"Characterization of\nHigh Explosives and Other Energetic Compounds by Computational Chemistry\nand Molecular Modeling","volume":"84","author":"Cramer","year":"2007","journal-title":"J. Chem. Educ."},{"key":"2026073109202612600_cit52","doi-asserted-by":"publisher","first-page":"8162","DOI":"10.1039\/c2dt30135k","article-title":"Quantifying Factors That Influence\nMetal Ion Release\nin Photocaged Complexes Using ZinCast Derivatives","volume":"41","author":"Gwizdala","year":"2012","journal-title":"Dalton Trans."},{"key":"2026073109202612600_cit53","doi-asserted-by":"publisher","first-page":"13622","DOI":"10.1021\/ja204935x","article-title":"Four-Coordinate,\n14-Electron RuII Complexes: Unusual Trigonal Pyramidal Geometry Enforced\nby Bis(Phosphino)Silyl Ligation","volume":"133","author":"MacInnis","year":"2011","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026073109202612600_cit54","doi-asserted-by":"publisher","first-page":"105","DOI":"10.1039\/c29710000105","article-title":"The Crystal Structure\nof a Trigonal Planar Copper(I)\nComplex","volume":"2","author":"Eller","year":"1971","journal-title":"J. Chem. Soc. Chem. Commun."},{"key":"2026073109202612600_cit55","doi-asserted-by":"publisher","first-page":"3230","DOI":"10.1021\/ja807081d","article-title":"Toluene and Ethylbenzene\nAliphatic C\u2013H Bond\nOxidations Initiated by a Dicopper(II)-\u03bc-1,2-Peroxo Complex","volume":"131","author":"Lucas","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"2026073109202612600_cit56","doi-asserted-by":"publisher","first-page":"1155","DOI":"10.1016\/j.ccr.2004.11.010","article-title":"Structural Aspects of Copper Catalyzed Atom Transfer\nRadical Polymerization","volume":"249","author":"Pintauer","year":"2005","journal-title":"Coord. Chem. 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