{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T15:54:25Z","timestamp":1792598065595,"version":"4.5.0"},"reference-count":70,"publisher":"American Chemical Society (ACS)","issue":"41","license":[{"start":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T00:00:00Z","timestamp":1791244800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T00:00:00Z","timestamp":1791244800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T00:00:00Z","timestamp":1791244800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100001691","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JP21H01952"],"award-info":[{"award-number":["JP21H01952"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001691","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JP21K05100"],"award-info":[{"award-number":["JP21K05100"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001691","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JP22KK0074"],"award-info":[{"award-number":["JP22KK0074"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001691","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JP23H03831"],"award-info":[{"award-number":["JP23H03831"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001691","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JP24K01500"],"award-info":[{"award-number":["JP24K01500"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001691","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JP24K01611"],"award-info":[{"award-number":["JP24K01611"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001691","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JP24KJ1799"],"award-info":[{"award-number":["JP24KJ1799"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001700","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JPMXP1726307494"],"award-info":[{"award-number":["JPMXP1726307494"]}],"id":[{"id":"10.13039\/501100001700","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100009023","name":"Ministry of Education, Culture, Sports, Science and Technology","doi-asserted-by":"publisher","award":["JPMJPR22QA"],"award-info":[{"award-number":["JPMJPR22QA"]}],"id":[{"id":"10.13039\/501100009023","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,21]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Previous studies on the hydrogen evolution reaction (HER) catalyzed by Pt(II)-based molecular catalysts have often demonstrated a second-order dependence of the HER rate on the catalyst concentration, suggesting the importance of stabilizing dinuclear platinum intermediates. However, some Pt(II)-based HER catalysts instead exhibit a first-order dependence, and the key factors governing this selection have received limited attention. Here, we discovered a new class of Pt(II)-based HER photocatalysts, abbreviated as [PtCl2(pBp)]2+, [Pt2Cl4(OpBp)]4+, and [Pt2Cl4(UpBp)]4+. Specifically, pBp2+ is a pyridinium-functionalized bipyridine, while OpBp4+ and UpBp4+ are dinucleating ligands wherein two pBp2+ fragments are doubly or singly bridged by phenylene moieties, respectively. Remarkably, all these photocatalysts exhibit two successive pBp2+-based 1-electron reductions with a potential separation of 290\u2013320 mV. These complexes serve as efficient photocatalysts for the aqueous-based HER at pH 5.0 in the presence of EDTA. Importantly, the HER rate exhibits a second-order dependence at lower concentrations, indicating that a 2-electron-reduced species is generated via a rate-determining disproportionation reaction (2Cat\u2013 \u2192 Cat + Cat2\u2013) and serves as a key intermediate for HER (Cat2\u2013 + 2H+ \u2192 Cat + H2). Conversely, a first-order dependence is observed at higher concentrations, where the rate-determining step shifts to the photoinduced electron transfer process. Notably, the Cat2\u2013 intermediate exists as a minor component (e.g., 0.2%) due to the large comproportionation constants. Nevertheless, this low-abundance species dictates the overall reaction rate because its HER pathway possesses a ca. 0.3 eV higher thermodynamic driving force than that doubly driven by the Cat\u2013\/Cat couple, rendering the process kinetically highly favorable.<\/jats:p>","DOI":"10.1021\/jacs.6c14800","type":"journal-article","created":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T10:01:21Z","timestamp":1791280881000},"page":"44854-44867","source":"Crossref","is-referenced-by-count":0,"title":["Concentration-Dependent\nTransition in the Rate-Determining\nStep of Hydrogen Evolution Driven by Pyridinium-Tethered Mononuclear\nand Dinuclear Platinum Photocatalysts"],"prefix":"10.1021","volume":"148","author":[{"given":"Fumika","family":"Sueyoshi","sequence":"first","affiliation":[{"name":"Kyushu University , , Motooka 744 , Nishi-Ku, ,","place":["Fukuoka, Japan, 819-0395"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5081-4825","authenticated-orcid":true,"given":"Kosei","family":"Yamauchi","sequence":"additional","affiliation":[{"name":"Kyushu University , , Motooka 744 , Nishi-Ku, ,","place":["Fukuoka, Japan, 819-0395"]},{"name":"Institute for Advanced Study, Kyushu University , Motooka 744 , Nishi-Ku, ,","place":["Fukuoka, Japan, 819-0395"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4976-9796","authenticated-orcid":true,"given":"Ken","family":"Sakai","sequence":"additional","affiliation":[{"name":"Kyushu University , , Motooka 744 , Nishi-Ku, ,","place":["Fukuoka, Japan, 819-0395"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,6]]},"reference":[{"key":"2026102111084392500_cit1a","doi-asserted-by":"publisher","first-page":"253","DOI":"10.1039\/B800489G","article-title":"Heterogeneous photocatalyst materials\nfor water splitting","volume":"38","author":"Kudo","year":"2009","journal-title":"Chem. Soc. Rev."},{"key":"2026102111084392500_cit1b","doi-asserted-by":"publisher","first-page":"2655","DOI":"10.1021\/jz1007966","article-title":"Photocatalytic Water Splitting: Recent\nProgress and Future Challenges","volume":"1","author":"Maeda","year":"2010","journal-title":"J. Phys. Chem.\nLett."},{"key":"2026102111084392500_cit1c","doi-asserted-by":"publisher","first-page":"14152","DOI":"10.1021\/jacs.6b09212","article-title":"Photoelectrochemical Reduction of CO2 Coupled\nto Water Oxidation Using a Photocathode with a Ru(II)\u2013Re(I)\nComplex Photocatalyst and a CoOx\/TaON Photoanode","volume":"138","author":"Sahara","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111084392500_cit1d","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202308956","article-title":"A Molecular Z-Scheme\nArtificial Photosynthetic System Under the Bias-Free Condition for\nCO2 Reduction Coupled with Two-electron Water Oxidation:\nPhotocatalytic Production of CO\/HCOOH and H2O2","volume":"62","author":"Kuttassery","year":"2023","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111084392500_cit2a","doi-asserted-by":"publisher","first-page":"4022","DOI":"10.1021\/cr050193e","article-title":"Hydrogen Production by Molecular\nPhotocatalysis","volume":"107","author":"Esswein","year":"2007","journal-title":"Chem. Rev."},{"key":"2026102111084392500_cit2b","doi-asserted-by":"publisher","first-page":"2338","DOI":"10.1039\/C2CS35334B","article-title":"Solar fuels generation and molecular\nsystems: is it homogeneous or heterogeneous catalysis?","volume":"42","author":"Artero","year":"2013","journal-title":"Chem. Soc. Rev."},{"key":"2026102111084392500_cit2c","doi-asserted-by":"publisher","first-page":"3808","DOI":"10.1039\/C4EE01709A","article-title":"Toward the rational benchmarking of homogeneous H2-evolving catalysts","volume":"7","author":"Artero","year":"2014","journal-title":"Energy Environ.\nSci."},{"key":"2026102111084392500_cit3a","doi-asserted-by":"publisher","first-page":"7501","DOI":"10.1039\/C3CS60405E","article-title":"Molecular\nartificial\nphotosynthesis","volume":"43","author":"Berardi","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"2026102111084392500_cit3b","doi-asserted-by":"publisher","first-page":"11863","DOI":"10.1021\/cr400572f","article-title":"Artificial\nPhotosynthesis: Molecular Systems for Catalytic Water Oxidation","volume":"114","author":"Ka\u0308rka\u0308s","year":"2014","journal-title":"Chem. Rev."},{"key":"2026102111084392500_cit3c","doi-asserted-by":"publisher","first-page":"197","DOI":"10.1016\/bs.adioch.2019.04.001","article-title":"Chapter Five\n- Mechanisms of water oxidation using ruthenium, cobalt, copper, and\niron molecular catalysts","volume":"74","author":"Parent","year":"2019","journal-title":"Adv. Inorg. Chem."},{"key":"2026102111084392500_cit4a","doi-asserted-by":"publisher","first-page":"1974","DOI":"10.1021\/ar900110c","article-title":"Development of Molecular\nElectrocatalysts\nfor CO2 Reduction and H2 Production\/Oxidation","volume":"42","author":"DuBois","year":"2009","journal-title":"Acc. Chem. Res."},{"key":"2026102111084392500_cit4b","doi-asserted-by":"publisher","first-page":"7238","DOI":"10.1002\/anie.201007987","article-title":"Splitting Water with Cobalt","volume":"50","author":"Artero","year":"2011","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111084392500_cit4c","doi-asserted-by":"publisher","first-page":"6763","DOI":"10.1039\/c2ee03309g","article-title":"Recent progress in electrochemical\nhydrogen production with earth-abundant metal complexes as catalysts","volume":"5","author":"Wang","year":"2012","journal-title":"Energy Environ. Sci."},{"key":"2026102111084392500_cit5a","doi-asserted-by":"publisher","first-page":"70","DOI":"10.1021\/acscatal.6b02181","article-title":"Electrons,\nPhotons, Protons, and Earth-Abundant Metal Complexes for Molecular\nCatalysis of CO2 Reduction","volume":"7","author":"Takeda","year":"2017","journal-title":"ACS Catal."},{"key":"2026102111084392500_cit5b","doi-asserted-by":"publisher","first-page":"4631","DOI":"10.1021\/acs.chemrev.7b00459","article-title":"Homogeneously Catalyzed Electroreduction\nof Carbon Dioxide\u2500Methods, Mechanisms, Catalysts","volume":"118","author":"Francke","year":"2018","journal-title":"Chem. Rev."},{"key":"2026102111084392500_cit6a","doi-asserted-by":"publisher","first-page":"7520","DOI":"10.1039\/C3CS60378D","article-title":"Recent advances\nin\nsemiconductors for photocatalytic and photoelectrochemical water splitting","volume":"43","author":"Hisatomi","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"2026102111084392500_cit6b","doi-asserted-by":"publisher","first-page":"568","DOI":"10.1007\/s11708-021-0774-8","article-title":"Visible light responsive photocatalysts developed by substitution\nwith metal cations aiming at artificial photosynthesis","volume":"15","author":"Yamaguchi","year":"2021","journal-title":"Front. Energy"},{"key":"2026102111084392500_cit7a","doi-asserted-by":"publisher","first-page":"1641","DOI":"10.1039\/C7SE00222J","article-title":"Visible-light-absorbing semiconductor\/molecular\ncatalyst hybrid photoelectrodes\nfor H2 or O2 evolution: recent advances and\nchallenges","volume":"1","author":"Wang","year":"2017","journal-title":"Sustainable Energy Fuels"},{"key":"2026102111084392500_cit7b","doi-asserted-by":"publisher","first-page":"11485","DOI":"10.1021\/jacs.6c01742","article-title":"A Fully Artificial\nMolecular-Based Photoelectrochemical Cell Enabling Overall Water Splitting\nby Combining a Photoanode and a Dark-Cathode","volume":"148","author":"Yan","year":"2026","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111084392500_cit8a","doi-asserted-by":"publisher","first-page":"169","DOI":"10.1080\/00958978808080702","article-title":"Photochemical Reduction of Water\nto Hydrogen Catalyzed by Mixed-Valent Tetranuclear Platinum Complex","volume":"18","author":"Sakai","year":"1988","journal-title":"J. Coord. Chem."},{"key":"2026102111084392500_cit8b","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/0304-5102(90)85235-A","article-title":"Homogeneous Catalysis of Platinum Blue Related Complexes\nin Photoreduction of Water into Hydrogen","volume":"62","author":"Sakai","year":"1990","journal-title":"J.\nMol. Catal."},{"key":"2026102111084392500_cit8c","doi-asserted-by":"publisher","first-page":"2753","DOI":"10.1016\/j.ccr.2007.08.014","article-title":"Homogeneous\ncatalysis of platinum(II) complexes in photochemical hydrogen production\nfrom water","volume":"251","author":"Sakai","year":"2007","journal-title":"Coord. Chem. Rev."},{"key":"2026102111084392500_cit8d","doi-asserted-by":"publisher","first-page":"1148","DOI":"10.1002\/chem.201002470","article-title":"Platinum(II)-Based Hydrogen-Evolving Catalysts Linked to Multipendant\nViologen Acceptors: Experimental and DFT Indications for Bimolecular\nPathways","volume":"17","author":"Ogawa","year":"2011","journal-title":"Chem.\u2500Eur. J."},{"key":"2026102111084392500_cit9a","doi-asserted-by":"publisher","first-page":"4127","DOI":"10.1021\/jo00300a033","article-title":"Isolation and Oxidation-Reduction\nof Methylviologen Cation Radicals. Novel Disproportionation in Charge-Transfer\nSalts by X-ray Crystallography","volume":"55","author":"Bockman","year":"1990","journal-title":"J. Org. Chem."},{"key":"2026102111084392500_cit9b","doi-asserted-by":"publisher","first-page":"8404","DOI":"10.1021\/ja902245e","article-title":"Evidence for Pt(II)-Based\nMolecular Catalysis in the Thermal Reduction of Water into Molecular\nHydrogen","volume":"131","author":"Yamauchi","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111084392500_cit10","doi-asserted-by":"publisher","first-page":"11218","DOI":"10.1039\/c0dt00741b","article-title":"Photochemical\nand Thermal Hydrogen Production from Water Catalyzed by Carboxylate-Bridged\nDirhodium(II) Complexes","volume":"39","author":"Tanaka","year":"2010","journal-title":"Dalton Trans."},{"key":"2026102111084392500_cit11a","doi-asserted-by":"publisher","first-page":"9872","DOI":"10.1039\/C4CC03493G","article-title":"A Cobalt-NHC\nComplex as an Improved Catalyst for Photochemical Hydrogen Evolution\nfrom Water","volume":"50","author":"Kawano","year":"2014","journal-title":"Chem. Commun."},{"key":"2026102111084392500_cit11b","doi-asserted-by":"publisher","first-page":"740","DOI":"10.1039\/D0SE01597K","article-title":"Improving the Overall Performance of Photochemical H2 Evolution\nCatalyzed by the Co-NHC Complex via the Redox Tuning of Electron Relays","volume":"5","author":"Yatsuzuka","year":"2021","journal-title":"Sustainable Energy Fuels"},{"key":"2026102111084392500_cit11c","doi-asserted-by":"publisher","first-page":"5602","DOI":"10.1021\/jacs.4c10246","article-title":"Viologen-Radical-Driven\nHydrogen Evolution from Water Catalyzed by Co-NHC Catalysts: Radical\nScavenging by Nitrate and Volmer-Heyrovsky-like CPET Pathway","volume":"147","author":"Yamauchi","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111084392500_cit12a","doi-asserted-by":"publisher","first-page":"4926","DOI":"10.1021\/ja058087h","article-title":"A Photo-Hydrogen-Evolving\nMolecular Device Driving Visible-Light-Induced EDTA-Reduction of Water\ninto Molecular Hydrogen","volume":"128","author":"Ozawa","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"2026102111084392500_cit12b","doi-asserted-by":"publisher","first-page":"920","DOI":"10.1246\/cl.2007.920","article-title":"An Effect of Structural Modification\nin the Photo-hydrogen-evolving RuIIPtII Dimers","volume":"36","author":"Ozawa","year":"2007","journal-title":"Chem. Lett."},{"key":"2026102111084392500_cit12c","doi-asserted-by":"publisher","first-page":"5868","DOI":"10.1039\/c0dt00077a","article-title":"Frontier Orbital Engineering\nof Photo-Hydrogen-Evolving Molecular Devices: a Clear Relationship\nBetween the H2-Evolving Activity and the Energy Level of\nthe LUMO","volume":"39","author":"Masaoka","year":"2010","journal-title":"Dalton Trans."},{"key":"2026102111084392500_cit12d","doi-asserted-by":"publisher","first-page":"1860","DOI":"10.1002\/asia.201000083","article-title":"Photo-Hydrogen-Evolving Molecular Catalysts Consisting of Polypyridyl\nRuthenium(II) Photosensitizers and Platinum(II) Catalysts: Insights\ninto the Reaction Mechanism","volume":"5","author":"Ozawa","year":"2010","journal-title":"Chem.\u2500Asian\nJ"},{"key":"2026102111084392500_cit12e","doi-asserted-by":"publisher","first-page":"4908","DOI":"10.3390\/molecules15074908","article-title":"Syntheses, Characterization,\nand Photo-Hydrogen-Evolving Properties of Tris(2,2\u2019-bipyridine)ruthenium(II)\nDerivatives Tethered to an H2-Evolving (2-phenylpyridinato)platinum(II)\nUnit","volume":"15","author":"Kobayashi","year":"2010","journal-title":"Molecules"},{"key":"2026102111084392500_cit12f","doi-asserted-by":"publisher","first-page":"2227","DOI":"10.1039\/c0cc04708b","article-title":"Photo-Hydrogen-Evolving Molecular\nDevices Driving Visible-Light-Induced Water Reduction into Molecular\nHydrogen: Structure-Activity Relationship and Reaction Mechanism","volume":"47","author":"Ozawa","year":"2011","journal-title":"Chem. Commun."},{"key":"2026102111084392500_cit12g","doi-asserted-by":"publisher","first-page":"3967","DOI":"10.1039\/c0dt01548b","article-title":"Syntheses, Characterization,\nand Photochemical Properties of Amidate-Bridged Pt(bpy) Dimers Tethered\nto Ru(bpy)32+ Derivatives","volume":"40","author":"Hirahara","year":"2011","journal-title":"Dalton Trans."},{"key":"2026102111084392500_cit12h","doi-asserted-by":"publisher","first-page":"3955","DOI":"10.1039\/c0dt01673j","article-title":"Light-Induced\nCharge Separation and Photocatalytic Hydrogen Evolution from Water\nusing RuIIPtII-Based Molecular Devices: Effects\nof Introducing Additional Donor and\/or Acceptor Sites","volume":"40","author":"Ajayakumar","year":"2011","journal-title":"Dalton Trans."},{"key":"2026102111084392500_cit12i","doi-asserted-by":"publisher","first-page":"1607","DOI":"10.1039\/C3CP54630F","article-title":"Mechanistic Studies of Photoinduced Intramolecular and Intermolecular\nElectron Transfer Processes in RuPt-centred Photo-hydrogen-evolving\nMolecular Devices","volume":"16","author":"Suneesh","year":"2014","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026102111084392500_cit12j","doi-asserted-by":"publisher","first-page":"5044","DOI":"10.1002\/anie.201409438","article-title":"Palladium versus Platinum: The Metal in the Catalytic Center of a\nMolecular Photocatalyst Determines the Mechanism of the Hydrogen Production\nwith Visible Light","volume":"54","author":"Pfeffer","year":"2015","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111084392500_cit13a","doi-asserted-by":"publisher","first-page":"6127","DOI":"10.1039\/b905610f","article-title":"Photo-Hydrogen-Evolving\nActivity of Chloro(terpyridine)platinum(II): a Single-Component Molecular\nPhotocatalyst","author":"Okazaki","year":"2009","journal-title":"Dalton Trans."},{"key":"2026102111084392500_cit13b","doi-asserted-by":"publisher","first-page":"4903","DOI":"10.1039\/c2dt12209j","article-title":"Synthesis, crystal structure, spectroscopic\nand electrochemical properties, and H2-evolving activity\nof a new [PtCl(terpyridine)]+ derivative with viologen-like\nredox properties","volume":"41","author":"Kobayashi","year":"2012","journal-title":"Dalton Trans."},{"key":"2026102111084392500_cit13c","doi-asserted-by":"publisher","first-page":"7431","DOI":"10.1002\/anie.201202720","article-title":"Photoinduced Hydrogen\nEvolution from Water Based on a Z-Scheme Photosynthesis by a Simple\nPlatinum(II) Terpyridine Derivative","volume":"51","author":"Kobayashi","year":"2012","journal-title":"Angew.\nChem., Int. Ed."},{"key":"2026102111084392500_cit13d","doi-asserted-by":"publisher","first-page":"8685","DOI":"10.1039\/C5DT00425J","article-title":"A tricarboxylated PtCl(terpyridine)\nderivative exhibiting pH-dependent photocatalytic activity for H2 evolution from water","volume":"44","author":"Yamauchi","year":"2015","journal-title":"Dalton Trans."},{"key":"2026102111084392500_cit13e","doi-asserted-by":"publisher","first-page":"10643","DOI":"10.1039\/C6DT01456A","article-title":"Improved Photocatalytic\nHydrogen Evolution Driven by Chloro(terpyridine)platinum(II) Derivatives\nTethered to a Single Pendant Viologen Acceptor","volume":"45","author":"Lin","year":"2016","journal-title":"Dalton Trans."},{"key":"2026102111084392500_cit14a","doi-asserted-by":"publisher","first-page":"4618","DOI":"10.1002\/anie.201311209","article-title":"Pigment-Acceptor-Catalyst\nTriads for Photochemical Hydrogen Evolution","volume":"53","author":"Kitamoto","year":"2014","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111084392500_cit14b","doi-asserted-by":"publisher","first-page":"14516","DOI":"10.1039\/C5CC03558A","article-title":"Pt(II)-Catalyzed\nPhotosynthesis for H2 Evolution Cycling Between Singly\nand Triply Reduced Species","volume":"51","author":"Yamamoto","year":"2015","journal-title":"Chem. Commun."},{"key":"2026102111084392500_cit14c","doi-asserted-by":"publisher","first-page":"1385","DOI":"10.1039\/C5CC08044D","article-title":"Photochemical H2 Evolution\nfrom Water Catalyzed by Dichloro(diphenylbipyridine)platinum(II) Derivative\nTethered to Multiple Viologen Acceptors","volume":"52","author":"Kitamoto","year":"2016","journal-title":"Chem.\nCommun."},{"key":"2026102111084392500_cit14d","doi-asserted-by":"publisher","first-page":"5183","DOI":"10.1039\/D1CC00903F","article-title":"Redox tuning\nin Pt(bpy)-viologen catalyst-acceptor dyads enabling photocatalytic\nhydrogen evolution from water","volume":"57","author":"Yatsuzuka","year":"2021","journal-title":"Chem. Commun."},{"key":"2026102111084392500_cit15a","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202418884","article-title":"Diplatinum Single-Molecular Photocatalyst Capable of Driving Hydrogen\nProduction from Water via Singlet-to-Triplet Transitions","volume":"64","author":"Kunikubo","year":"2025","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026102111084392500_cit15b","doi-asserted-by":"publisher","first-page":"22580","DOI":"10.1039\/D5SC06457K","article-title":"Enhanced Red-Light-Driven Hydrogen Evolution by a Diplatinum Photocatalyst\nby the Larger Wavefunction Leakage of Iodide Coordinated to the Platinum\nCenter","volume":"16","author":"Kunikubo","year":"2025","journal-title":"Chem. Sci."},{"key":"2026102111084392500_cit16","unstructured":"Wakiyama, F.\n          \n          Ph.D. Thesis; Kyushu University, 2021."},{"key":"2026102111084392500_cit17a","doi-asserted-by":"publisher","first-page":"18873","DOI":"10.1021\/jp3059799","article-title":"Intercalation\nof Pt(II) Terpyridine Complexes into\nLayered K4Nb6O17 and Visible-Light-Driven\nPhotocatalytic Production of H2","volume":"116","author":"Mori","year":"2012","journal-title":"J. Phys. Chem. C"},{"key":"2026102111084392500_cit17b","doi-asserted-by":"publisher","first-page":"3229","DOI":"10.1039\/c3ee41548a","article-title":"Post-synthesis modification of a\nmetal\u2013organic framework to construct a bifunctional photocatalyst\nfor hydrogen production","volume":"6","author":"Zhou","year":"2013","journal-title":"Energy Environ. Sci."},{"key":"2026102111084392500_cit17c","doi-asserted-by":"publisher","first-page":"15347","DOI":"10.1039\/D1SC03743A","article-title":"Enhanced photoreduction\nof water catalyzed by a cucurbit[8]uril-secured platinum dimer","volume":"12","author":"Rabbani","year":"2021","journal-title":"Chem. Sci."},{"key":"2026102111084392500_cit18","doi-asserted-by":"publisher","first-page":"5084","DOI":"10.1021\/ic00050a030","article-title":"Electrochemistry\nand Spectroelectrochemistry\n(EPR, UV-Vis-Near-IR) of Platinum(II) 2,2\u2019-Bipyridine and Ring-Metalated\nBipyridine Complexes: PtII(L\u2013) and PtI(L\u2013) but Not PtI(L)","volume":"31","author":"Braterman","year":"1992","journal-title":"Inorg. Chem."},{"key":"2026102111084392500_cit19","doi-asserted-by":"publisher","first-page":"4441","DOI":"10.1039\/D5SE00423C","article-title":"Effect of ancillary ligand substitution\non photocatalytic hydrogen production","volume":"9","author":"Gupta","year":"2025","journal-title":"Sustainable\nEnergy Fuels"},{"key":"2026102111084392500_cit20","doi-asserted-by":"publisher","first-page":"267","DOI":"10.1002\/chem.201101998","article-title":"Construction of\nMetal\u2013Organic Frameworks: Versatile\nBehaviour of a Ligand Containing Mono- and Bidentate Coordination\nSites","volume":"18","author":"Jacobs","year":"2012","journal-title":"Chem.\u2500Eur. J."},{"key":"2026102111084392500_cit21","doi-asserted-by":"publisher","first-page":"1280","DOI":"10.1021\/ic50112a025","article-title":"Palladium(II) and\nPlatinum(II) Alkyl Sulfoxide Complexes. Examples of Sulfur-Bonded,\nMixed Sulfur- and Oxygen-Bonded, and Totally Oxygen-Bonded Complexes","volume":"11","author":"Price","year":"1972","journal-title":"Inorg. Chem."},{"key":"2026102111084392500_cit22","doi-asserted-by":"publisher","first-page":"x250517","DOI":"10.1107\/S2414314625005176","article-title":"4,4\u2019-{[(2,2\u2019-Bipyridine)-5,5\u2032-dicarbonyl]bis(azanediyl)}bis(1-methylpyridin-1-ium)\nbis[hexafluoridophosphate(V)] acetonitrile disolvate","volume":"10","author":"Sueyoshi","year":"2025","journal-title":"IUCrData"},{"key":"2026102111084392500_cit23","unstructured":"CrysAlis PRO; Rigaku Oxford Diffraction, Yarnton,\nU.K., 2024."},{"key":"2026102111084392500_cit24","first-page":"3","article-title":"Integrated\nspace-group and crystal structure determination","volume":"A71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr."},{"key":"2026102111084392500_cit25","doi-asserted-by":"publisher","first-page":"3","DOI":"10.1107\/S2053229614024218","article-title":"Crystal\nstructure refinement with SHELXL","volume":"C71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr."},{"key":"2026102111084392500_cit26","unstructured":"Sakai, K.\n          \n          KENX; Kyushu University: Japan, 2026."},{"key":"2026102111084392500_cit27","unstructured":"Molecular Structure Corporation, TEXSAN Version\n1.11r1, MSC,\n3200 Research Forest Drive; Woodlands, 2001."},{"key":"2026102111084392500_cit28","unstructured":"Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; et al.; Gaussian\n16, Revision C.01; Gaussian, Inc.: Wallingford CT, 2016."},{"key":"2026102111084392500_cit29a","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 suite of\ndensity functionals for main group thermochemistry, thermochemical\nkinetics, noncovalent interactions, excited states, and transition\nelements: two new functionals and systematic testing of four M06-class\nfunctionals and 12 other functionals","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor.\nChem. Acc."},{"key":"2026102111084392500_cit29b","doi-asserted-by":"publisher","first-page":"1095","DOI":"10.1021\/jp7109127","article-title":"How Well\nCan New-Generation Density Functionals Describe the Energetics of\nBond-Dissociation Reactions Producing Radicals","volume":"112","author":"Zhao","year":"2008","journal-title":"J. Phys. Chem. A"},{"key":"2026102111084392500_cit29c","doi-asserted-by":"publisher","first-page":"157","DOI":"10.1021\/ar700111a","article-title":"Density Functionals with Broad Applicability in Chemistry","volume":"41","author":"Zhao","year":"2008","journal-title":"Acc. Chem. Res."},{"key":"2026102111084392500_cit30a","doi-asserted-by":"publisher","first-page":"1995","DOI":"10.1021\/jp9716997","article-title":"Quantum Calculation\nof Molecular Energies and Energy Gradients in Solution by a Conductor\nSolvent Model","volume":"102","author":"Barone","year":"1998","journal-title":"J. Phys. Chem. A"},{"key":"2026102111084392500_cit30b","doi-asserted-by":"publisher","first-page":"669","DOI":"10.1002\/jcc.10189","article-title":"Energies,\nstructures, and electronic properties of molecules in solution with\nthe C-PCM solvation model","volume":"24","author":"Cossi","year":"2003","journal-title":"J. Comput. Chem."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c14800","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/41\/44854\/68752869\/jacs.6c14800.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/41\/44854\/68752869\/jacs.6c14800.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T15:15:41Z","timestamp":1792595741000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/41\/44854\/5444985\/Concentration-Dependent-Transition-in-the-Rate"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,6]]},"references-count":70,"journal-issue":{"issue":"41","published-online":{"date-parts":[[2026,10,6]]},"published-print":{"date-parts":[[2026,10,21]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c14800","relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.15006300\/v1","asserted-by":"object"},{"id-type":"doi","id":"10.26434\/chemrxiv.15006300\/v2","asserted-by":"object"}]},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,6]]}}}