{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,30]],"date-time":"2026-08-30T17:22:30Z","timestamp":1788110550999,"version":"build-2803163510"},"reference-count":67,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2026,3,31]],"date-time":"2026-03-31T00:00:00Z","timestamp":1774915200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,3,31]],"date-time":"2026-03-31T00:00:00Z","timestamp":1774915200000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemSusChem"],"published-print":{"date-parts":[[2026,4,14]]},"abstract":"<jats:p>\n                    The design and development of bioinspired coordination compounds are crucial for laying the foundation to deliver low\u2010cost, energy\u2010efficient materials that promote energy sustainability. In this work, isostructural copper complexes, Cu\u2010L\n                    <jats:sub>N2S2<\/jats:sub>\n                    and Cu\u2010L\n                    <jats:sub>N3S<\/jats:sub>\n                    , in tune with the donor centers in the ligand backbone, (L\n                    <jats:sub>N2S2<\/jats:sub>\n                    \u2009=\u20091,2\u2010bis((pyridin\u20102\u2010ylmethyl)thio)ethane and L\n                    <jats:sub>N3S<\/jats:sub>\n                    =N\u2010(pyridin\u20102\u2010ylmethyl)\u20102\u2010((pyridine\u20102\u2010ylmethyl)thio)ethane\u20101\u2010amine) have been prepared, structurally characterized, and evaluated for their electrocatalytic fate towards the sustainable hydrogen production activities in water. Single\u2010crystal X\u2010ray crystallography reveals that the copper centers in both complexes adopt a distorted square pyramidal geometry. Cu\u2010L\n                    <jats:sub>N2S2<\/jats:sub>\n                    exhibits superior electrocatalytic performance over Cu\u2010L\n                    <jats:sub>N3S<\/jats:sub>\n                    in acidic aqueous media, achieving an outstanding turnover frequency (TOF) of 2.90\u2009\u00d7\u200910\n                    <jats:sup>3<\/jats:sup>\n                    \u2009s\n                    <jats:sup>\u22121<\/jats:sup>\n                    with 96% Faradaic efficiency. Detailed mechanistic insights, supported by spectroscopic, analytical, and DFT calculations, reveal divergent HER pathways: Cu\u2010L\n                    <jats:sub>N3S<\/jats:sub>\n                    follows an ECEC mechanism, while Cu\u2010L\n                    <jats:sub>N2S2<\/jats:sub>\n                    operates via a CECE sequence. Protonation and reduction site analyses highlight the critical role of mixed hard\u2013soft donor environments in modulating redox behavior and promoting hydride formation for efficient hydrogen production. The greater structural distortion arises from the higher number of sulfur donors in the ligand environment of Cu\u2010L\n                    <jats:sub>\n                      <jats:bold>N2S2<\/jats:bold>\n                    <\/jats:sub>\n                    , which in turn promotes the formation of the observed coordination geometry feasible for sustainable electrocatalytic evolution of hydrogen in water.\n                  <\/jats:p>","DOI":"10.1002\/cssc.202502322","type":"journal-article","created":{"date-parts":[[2026,4,1]],"date-time":"2026-04-01T06:35:21Z","timestamp":1775025321000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Bioinspired Copper(II) Complexes With N,S\u2010Donor Ligands: Structure\u2013Activity Relationships and Mechanistic Insights for Aqueous Hydrogen Evolution Reaction"],"prefix":"10.1002","volume":"19","author":[{"given":"Madhumita","family":"Samanta","sequence":"first","affiliation":[{"name":"Laboratory of Structural Engineering &amp; Sustainable Catalysis Department of Chemistry University of North Bengal  Darjeeling India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sangharaj","family":"Diyali","sequence":"additional","affiliation":[{"name":"Laboratory of Structural Engineering &amp; Sustainable Catalysis Department of Chemistry University of North Bengal  Darjeeling India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1064-8308","authenticated-orcid":false,"given":"Nilankar","family":"Diyali","sequence":"additional","affiliation":[{"name":"Laboratory of Structural Engineering &amp; Sustainable Catalysis Department of Chemistry University of North Bengal  Darjeeling India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Subhajit","family":"Saha","sequence":"additional","affiliation":[{"name":"Laboratory of Structural Engineering &amp; Sustainable Catalysis Department of Chemistry University of North Bengal  Darjeeling India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Suraj Kumar","family":"Agrawalla","sequence":"additional","affiliation":[{"name":"School of Chemical Sciences National Institute of Science Education and Research  Bhubaneswar India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"family":"Sakshi","sequence":"additional","affiliation":[{"name":"Department of Chemical Sciences Indian Institute of Science Education and Research, Mohali  Mohali Punjab India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Angshuman Roy","family":"Choudhury","sequence":"additional","affiliation":[{"name":"Department of Chemical Sciences Indian Institute of Science Education and Research, Mohali  Mohali Punjab India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chandra Shekhar","family":"Purohit","sequence":"additional","affiliation":[{"name":"School of Chemical Sciences National Institute of Science Education and Research  Bhubaneswar India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5447-9729","authenticated-orcid":false,"given":"Bhaskar","family":"Biswas","sequence":"additional","affiliation":[{"name":"Laboratory of Structural Engineering &amp; Sustainable Catalysis Department of Chemistry University of North Bengal  Darjeeling India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,3,31]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.langmuir.5c03927"},{"key":"e_1_2_9_3_1","first-page":"1","article-title":"Challenges and Emerging Trends in Hydrogen Energy Industrialization: From Hydrogen Evolution Reaction to Storage, Transportation, and Utilization","volume":"21","author":"Xu S.","year":"2025","journal-title":"Small"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.enrev.2025.100154"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.3390\/eng6040081"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.3390\/membranes12020173"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2023.215496"},{"key":"e_1_2_9_8_1","doi-asserted-by":"crossref","unstructured":"T.Asamoah A.Antwi E.Doku K.Asare M.Nartey andK.Mensah\u2010Darkwa MoS2 as a Bifunctional Electrocatalyst for Water Splitting (2024):https:\/\/doi.org\/10.26434\/chemrxiv\u20102024\u2010mhgmj.","DOI":"10.26434\/chemrxiv-2024-mhgmj"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3NR01836A"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.8b06045"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2575"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00180"},{"key":"e_1_2_9_13_1","first-page":"1","article-title":"Insights on Forming N, O\u2010Coordinated Cu Single\u2010Atom Catalysts for Electrochemical Reduction CO2 to Methane","volume":"12","author":"Cai Y.","year":"2021","journal-title":"Nature Communications"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.electacta.2020.136614"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.4c01043"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202404396"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic500069c"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b01707"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201804661"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.cgd.4c00144"},{"key":"e_1_2_9_21_1","doi-asserted-by":"crossref","unstructured":"S.Diyali N.Diyali M.Samanta et al. Chem. Asian J.20(2025):e202500203 https:\/\/doi.org\/10.1002\/asia.202500203.","DOI":"10.1002\/asia.202500203"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.8b00881"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.8b02110"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201700590"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1710443114"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsaem.5c01390"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c03819"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.4c20152"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b10407"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CY02253K"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b02157"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4DT01358A"},{"key":"e_1_2_9_33_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010024\u201047061\u20106"},{"key":"e_1_2_9_34_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ijhydene.2023.12.237"},{"key":"e_1_2_9_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.1c05538"},{"key":"e_1_2_9_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.6b09975"},{"key":"e_1_2_9_37_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0QI01247E"},{"key":"e_1_2_9_38_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6DT00082G"},{"key":"e_1_2_9_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/cplu.202300679"},{"key":"e_1_2_9_40_1","doi-asserted-by":"publisher","DOI":"10.4236\/ajac.2018.91002"},{"key":"e_1_2_9_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.2c00102"},{"key":"e_1_2_9_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.analchem.6b01637"},{"key":"e_1_2_9_43_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3CS00727H"},{"key":"e_1_2_9_44_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2021.115425"},{"key":"e_1_2_9_45_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.7b01608"},{"key":"e_1_2_9_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b00045"},{"key":"e_1_2_9_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja207842r"},{"key":"e_1_2_9_48_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1120757109"},{"key":"e_1_2_9_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b00045"},{"key":"e_1_2_9_50_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ijhydene.2014.07.030"},{"key":"e_1_2_9_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.3c00667"},{"key":"e_1_2_9_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.0c00555"},{"key":"e_1_2_9_53_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.202401089"},{"key":"e_1_2_9_54_1","doi-asserted-by":"publisher","DOI":"10.1002\/slct.201702113"},{"key":"e_1_2_9_55_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4SE00953C"},{"key":"e_1_2_9_56_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2RA05133H"},{"key":"e_1_2_9_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/ed083p1229"},{"key":"e_1_2_9_58_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules29102245"},{"key":"e_1_2_9_59_1","doi-asserted-by":"publisher","DOI":"10.1021\/cs300019h"},{"key":"e_1_2_9_60_1","doi-asserted-by":"publisher","DOI":"10.1021\/ac60210a007"},{"key":"e_1_2_9_61_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1NJ06003A"},{"key":"e_1_2_9_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja067876b"},{"key":"e_1_2_9_63_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b02586"},{"key":"e_1_2_9_64_1","volume-title":"Ionization Constants of Organic Acids in Aqueous Solution","author":"Serjeant E. P.","year":"1979"},{"key":"e_1_2_9_65_1","doi-asserted-by":"publisher","DOI":"10.1039\/B311053B"},{"key":"e_1_2_9_66_1","doi-asserted-by":"publisher","DOI":"10.1039\/DT9900000891"},{"key":"e_1_2_9_67_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcb.0c04231"},{"key":"e_1_2_9_68_1","doi-asserted-by":"publisher","DOI":"10.1021\/ed081p1350"}],"container-title":["ChemSusChem"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cssc.202502322","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/cssc.202502322","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cssc.202502322","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,8]],"date-time":"2026-08-08T18:13:29Z","timestamp":1786212809000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/cssc.202502322"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,3,31]]},"references-count":67,"journal-issue":{"issue":"7","published-print":{"date-parts":[[2026,4,14]]}},"alternative-id":["10.1002\/cssc.202502322"],"URL":"https:\/\/doi.org\/10.1002\/cssc.202502322","archive":["Portico"],"relation":{},"ISSN":["1864-5631","1864-564X"],"issn-type":[{"value":"1864-5631","type":"print"},{"value":"1864-564X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,3,31]]},"assertion":[{"value":"2025-10-19","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-02-13","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-03-31","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202502322"}}