{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,11]],"date-time":"2026-01-11T00:30:56Z","timestamp":1768091456188,"version":"3.49.0"},"reference-count":46,"publisher":"International Union of Crystallography (IUCr)","issue":"6","license":[{"start":{"date-parts":[[2021,10,7]],"date-time":"2021-10-07T00:00:00Z","timestamp":1633564800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/journals.iucr.org\/services\/copyrightpolicy.html"},{"start":{"date-parts":[[2021,10,7]],"date-time":"2021-10-07T00:00:00Z","timestamp":1633564800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/journals.iucr.org\/services\/copyrightpolicy.html#TDM"}],"funder":[{"DOI":"10.13039\/501100000038","name":"Natural Sciences and Engineering Research Council of Canada","doi-asserted-by":"publisher","award":["RGPIN 2016-04546"],"award-info":[{"award-number":["RGPIN 2016-04546"]}],"id":[{"id":"10.13039\/501100000038","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Canadian Foundation for Innovation"},{"name":"Province of Alberta"},{"DOI":"10.13039\/100000892","name":"Prostate Cancer Foundation","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100000892","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100006132","name":"U.S. Department of Energy, Office of Science","doi-asserted-by":"publisher","award":["DE-AC02-76SF00515"],"award-info":[{"award-number":["DE-AC02-76SF00515"]}],"id":[{"id":"10.13039\/100006132","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000057","name":"National Institutes of Health, National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["P41GM103393"],"award-info":[{"award-number":["P41GM103393"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["iucr.org","wiley.com","iucrj.org"],"crossmark-restriction":true},"short-container-title":["J Synchrotron Rad","J Synchrotron Radiat"],"accepted":{"date-parts":[[2021,8,12]]},"published-print":{"date-parts":[[2021,11,1]]},"abstract":"<jats:p>Sulfur <jats:italic>K<\/jats:italic>-edge X-ray absorption spectroscopy (XAS) was employed to experimentally characterize the coordinative bond between the thiourea (TU) or thiocarbamide ligand and transition metal (TM) ions Zn<jats:sup>2+<\/jats:sup>, Co<jats:sup>2+<\/jats:sup> and Ni<jats:sup>2+<\/jats:sup> in distorted tetrahedral and octahedral homoleptic coordination environments. Comparisons of XAS spectra of the free TU ligand and [Zn(TU)<jats:sub>4<\/jats:sub>]<jats:sup>2+<\/jats:sup>, [Co(TU)<jats:sub>4<\/jats:sub>]<jats:sup>2+<\/jats:sup> and [Ni(TU)<jats:sub>6<\/jats:sub>]<jats:sup>2+<\/jats:sup> complexes clearly identify spectral features unique to TM<jats:sup>2+<\/jats:sup>\u2013S(TU) bonding. Quantitative analysis of pre-edge intensities describes the covalency of Ni<jats:sup>2+<\/jats:sup>\u2014S(TU) and Co<jats:sup>2+<\/jats:sup>\u2014S(TU) bonding to be at most 21% and 9% as expressed by the S 3<jats:italic>p<\/jats:italic> contributions per TM 3<jats:italic>d<\/jats:italic> electron hole. Using relevant Ni<jats:sup>2+<\/jats:sup> complexes with dithiocarbamate and thioether ligands, we evaluated the empirical S 1<jats:italic>s<\/jats:italic> \u2192 3<jats:italic>p<\/jats:italic> transition dipole integrals developed for S-donor ligands and their dependence on heteroatom substitutions. With the aid of density functional theory-based ground electronic state calculations, we found evidence for the need of using a transition dipole that is dependent on the presence of conjugated heteroatom (N) substitution in these S-donor ligands.<\/jats:p>","DOI":"10.1107\/s1600577521008389","type":"journal-article","created":{"date-parts":[[2021,10,7]],"date-time":"2021-10-07T17:04:34Z","timestamp":1633626274000},"page":"1825-1838","update-policy":"https:\/\/doi.org\/10.1107\/cm_01","source":"Crossref","is-referenced-by-count":3,"title":["Ground electronic state description of thiourea coordination in homoleptic Zn<sup>2+<\/sup>, Ni<sup>2+<\/sup> and Co<sup>2+<\/sup> complexes using sulfur <i>K<\/i>-edge X-ray absorption spectroscopy"],"prefix":"10.1107","volume":"28","author":[{"given":"Matt S.","family":"Queen","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6298-8187","authenticated-orcid":true,"given":"Farideh","family":"Jalilehvand","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9314-6222","authenticated-orcid":true,"given":"Robert K.","family":"Szilagyi","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"329","published-online":{"date-parts":[[2021,10,7]]},"reference":[{"key":"hf5424_bb1","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1021\/ar00109a003","volume":"18","author":"Bader","year":"1985","journal-title":"Acc. Chem. Res."},{"key":"hf5424_bb2","doi-asserted-by":"crossref","first-page":"7431","DOI":"10.1021\/jp102748b","volume":"114","author":"Bader","year":"2010","journal-title":"J. Phys. Chem. A"},{"key":"hf5424_bb3","doi-asserted-by":"crossref","first-page":"3098","DOI":"10.1103\/PhysRevA.38.3098","volume":"38","author":"Becke","year":"1988","journal-title":"Phys. Rev. A"},{"key":"hf5424_bb4","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"hf5424_bb5","doi-asserted-by":"crossref","first-page":"633","DOI":"10.1016\/j.ccr.2004.08.022","volume":"249","author":"Cortesguzman","year":"2005","journal-title":"Coord. Chem. Rev."},{"key":"hf5424_bb6","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1016\/0009-2614(96)00349-1","volume":"255","author":"Cossi","year":"1996","journal-title":"Chem. Phys. Lett."},{"key":"hf5424_bb7","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1021\/ic50011a004","volume":"3","author":"Cotton","year":"1964","journal-title":"Inorg. Chem."},{"key":"hf5424_bb8","doi-asserted-by":"crossref","first-page":"101","DOI":"10.1016\/S0924-2031(02)00099-1","volume":"31","author":"El-Bahy","year":"2003","journal-title":"Vib. Spectrosc."},{"key":"hf5424_bb9","doi-asserted-by":"crossref","first-page":"1571","DOI":"10.1002\/(SICI)1096-987X(199610)17:13<1571::AID-JCC9>3.0.CO;2-P","volume":"17","author":"Feller","year":"1996","journal-title":"J. Comput. Chem."},{"key":"hf5424_bb10","doi-asserted-by":"crossref","first-page":"7211","DOI":"10.1021\/ja00544a007","volume":"102","author":"Foster","year":"1980","journal-title":"J. Am. Chem. Soc."},{"key":"hf5424_bb11","unstructured":"Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A. Jr, Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, N. J., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, \u00d6., Foresman, J. B., Ortiz, J. V., Cioslowski, J. & Fox, D. J. (2009). Gaussian 09. Revision C1. Gaussian Inc., Wallingford, Connecticut, USA."},{"key":"hf5424_bb12","first-page":"A4","volume":"127","author":"Fritz","year":"1994","journal-title":"Chem. Ber."},{"key":"hf5424_bb13","unstructured":"Gardenghi, D. J. (2011). ADRP - Automated Data Reduction Protocol. Montana State University, Bozeman, MT, USA."},{"key":"hf5424_bb14","doi-asserted-by":"crossref","first-page":"2677","DOI":"10.1002\/ejic.201100318","volume":"2011","author":"Giles","year":"2011","journal-title":"Eur. J. Inorg. Chem."},{"key":"hf5424_bb15","doi-asserted-by":"crossref","first-page":"1643","DOI":"10.1021\/ja00160a062","volume":"112","author":"Hedman","year":"1990","journal-title":"J. Am. Chem. Soc."},{"key":"hf5424_bb16","unstructured":"Keith, T. A. (2011). AIMAll. TK Gristmill Software, Overland Park, KS, USA. http:\/\/aim.tkgristmill.com\/."},{"key":"hf5424_bb17","doi-asserted-by":"crossref","first-page":"484","DOI":"10.1107\/S0909049509021384","volume":"16","author":"Kennepohl","year":"2009","journal-title":"J. Synchrotron Rad."},{"key":"hf5424_bb18","doi-asserted-by":"crossref","first-page":"1944","DOI":"10.1021\/ja01260a054","volume":"64","author":"Kumler","year":"1942","journal-title":"J. Am. Chem. Soc."},{"key":"hf5424_bb19","doi-asserted-by":"crossref","first-page":"2626","DOI":"10.1107\/S0567740882009480","volume":"38","author":"Kutoglu","year":"1982","journal-title":"Acta Cryst. B"},{"key":"hf5424_bb20","doi-asserted-by":"crossref","first-page":"785","DOI":"10.1103\/PhysRevB.37.785","volume":"37","author":"Lee","year":"1988","journal-title":"Phys. Rev. B"},{"key":"hf5424_bb21","doi-asserted-by":"crossref","first-page":"5151","DOI":"10.1063\/1.473558","volume":"106","author":"Mennucci","year":"1997","journal-title":"J. Chem. Phys."},{"key":"hf5424_bb22","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1016\/0301-0104(81)85090-2","volume":"55","author":"Miertu\u0161","year":"1981","journal-title":"Chem. Phys."},{"key":"hf5424_bb23","doi-asserted-by":"crossref","first-page":"4854","DOI":"10.1021\/ic990461p","volume":"38","author":"Neese","year":"1999","journal-title":"Inorg. Chem."},{"key":"hf5424_bb24","doi-asserted-by":"crossref","first-page":"1547","DOI":"10.1021\/jz500260s","volume":"5","author":"Pascal","year":"2014","journal-title":"J. Phys. Chem. Lett."},{"key":"hf5424_bb25","doi-asserted-by":"crossref","first-page":"1127","DOI":"10.1002\/jcc.540151009","volume":"15","author":"Pascual-ahuir","year":"1994","journal-title":"J. Comput. Chem."},{"key":"hf5424_bb26","doi-asserted-by":"crossref","first-page":"8822","DOI":"10.1103\/PhysRevB.33.8822","volume":"33","author":"Perdew","year":"1986","journal-title":"Phys. Rev. B"},{"key":"hf5424_bb27","doi-asserted-by":"crossref","first-page":"902","DOI":"10.1021\/ct800531s","volume":"5","author":"Perdew","year":"2009","journal-title":"J. Chem. Theory Comput."},{"key":"hf5424_bb28","doi-asserted-by":"crossref","first-page":"564","DOI":"10.1016\/j.ccr.2012.07.020","volume":"257","author":"Queen","year":"2013","journal-title":"Coord. Chem. Rev."},{"key":"hf5424_bb29","doi-asserted-by":"crossref","first-page":"3513","DOI":"10.1021\/ic2022769","volume":"51","author":"Rokhsana","year":"2012","journal-title":"Inorg. Chem."},{"key":"hf5424_bb30","doi-asserted-by":"crossref","first-page":"1045","DOI":"10.1021\/ci600510j","volume":"47","author":"Schuchardt","year":"2007","journal-title":"J. Chem. Inf. Model."},{"key":"hf5424_bb31","doi-asserted-by":"crossref","first-page":"155","DOI":"10.1016\/0022-328X(94)88068-9","volume":"469","author":"Seitz","year":"1994","journal-title":"J. Organomet. Chem."},{"key":"hf5424_bb32","doi-asserted-by":"crossref","first-page":"2259","DOI":"10.1021\/ja00113a015","volume":"117","author":"Shadle","year":"1995","journal-title":"J. Am. Chem. Soc."},{"key":"hf5424_bb33","doi-asserted-by":"crossref","first-page":"767","DOI":"10.1021\/ja00055a057","volume":"115","author":"Shadle","year":"1993","journal-title":"J. Am. Chem. Soc."},{"key":"hf5424_bb34","doi-asserted-by":"crossref","first-page":"97","DOI":"10.1016\/j.ccr.2004.03.020","volume":"249","author":"Solomon","year":"2005","journal-title":"Coord. Chem. Rev."},{"key":"hf5424_bb35","doi-asserted-by":"crossref","first-page":"235","DOI":"10.1007\/BF01570985","volume":"6","author":"Spofford","year":"1976","journal-title":"J. Cryst. Mol. Struct."},{"key":"hf5424_bb36","doi-asserted-by":"crossref","first-page":"075102","DOI":"10.1103\/PhysRevB.69.075102","volume":"69","author":"Staroverov","year":"2004","journal-title":"Phys. Rev. B"},{"key":"hf5424_bb37","unstructured":"Szilagyi, R. K. (2009). Encyclopedia of Inorganic Chemistry, 2nd ed., edited by B. R. King, pp. 1-13. John Wiley."},{"key":"hf5424_bb38","doi-asserted-by":"crossref","first-page":"2994","DOI":"10.1021\/jp014121c","volume":"106","author":"Szilagyi","year":"2002","journal-title":"J. Phys. Chem. A"},{"key":"hf5424_bb39","doi-asserted-by":"crossref","first-page":"146401","DOI":"10.1103\/PhysRevLett.91.146401","volume":"91","author":"Tao","year":"2003","journal-title":"Phys. Rev. Lett."},{"key":"hf5424_bb40","doi-asserted-by":"crossref","first-page":"2999","DOI":"10.1021\/cr9904009","volume":"105","author":"Tomasi","year":"2005","journal-title":"Chem. Rev."},{"key":"hf5424_bb41","doi-asserted-by":"crossref","first-page":"2297","DOI":"10.1107\/S0567740878007955","volume":"34","author":"Vega","year":"1978","journal-title":"Acta Cryst. B"},{"key":"hf5424_bb42","doi-asserted-by":"crossref","first-page":"4638","DOI":"10.1021\/ic00024a035","volume":"30","author":"Watson","year":"1991","journal-title":"Inorg. Chem."},{"key":"hf5424_bb43","doi-asserted-by":"crossref","first-page":"3297","DOI":"10.1039\/b508541a","volume":"7","author":"Weigend","year":"2005","journal-title":"Phys. Chem. Chem. Phys."},{"key":"hf5424_bb44","doi-asserted-by":"crossref","first-page":"424","DOI":"10.1021\/ic50073a004","volume":"8","author":"Weininger","year":"1969","journal-title":"Inorg. Chem."},{"key":"hf5424_bb45","doi-asserted-by":"crossref","first-page":"A18","DOI":"10.1149\/2.1441614jes","volume":"164","author":"Wujcik","year":"2017","journal-title":"J. Electrochem. Soc."},{"key":"hf5424_bb46","doi-asserted-by":"crossref","first-page":"527","DOI":"10.1021\/ja01536a005","volume":"80","author":"Yamaguchi","year":"1958","journal-title":"J. Am. Chem. Soc."}],"container-title":["Journal of Synchrotron Radiation"],"original-title":[],"link":[{"URL":"http:\/\/journals.iucr.org\/s\/issues\/2021\/06\/00\/hf5424\/hf5424.pdf","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"http:\/\/journals.iucr.org\/s\/issues\/2021\/06\/00\/hf5424\/hf5424.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,1,13]],"date-time":"2025-01-13T10:40:22Z","timestamp":1736764822000},"score":1,"resource":{"primary":{"URL":"https:\/\/journals.iucr.org\/paper?S1600577521008389"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,10,7]]},"references-count":46,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2021,11]]}},"alternative-id":["S1600577521008389"],"URL":"https:\/\/doi.org\/10.1107\/s1600577521008389","relation":{"is-supplemented-by":[{"id-type":"doi","id":"10.1107\/S1600577521008389\/hf5424sup1.pdf","asserted-by":"subject"},{"id-type":"doi","id":"10.5281\/zenodo.4770724","asserted-by":"subject"}]},"ISSN":["1600-5775"],"issn-type":[{"value":"1600-5775","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,10,7]]},"assertion":[{"value":"Journal of Synchrotron Radiation","order":0,"name":"journal","label":"Publication","explanation":{"URL":"http:\/\/journals.iucr.org\/s"},"group":{"name":"general","label":"General"}},{"value":"research papers","order":1,"name":"content_type","label":"Content type","explanation":{"URL":"https:\/\/journals.iucr.org\/s\/services\/notesforauthors.html"},"group":{"name":"general","label":"General"}},{"value":"Available","URL":"https:\/\/scripts.iucr.org\/cgi-bin\/citedin?hf5424","order":2,"name":"article_metrics","label":"Article metrics","group":{"name":"general","label":"General"}},{"value":"Yes","order":0,"name":"peer_reviewed","label":"Peer reviewed","group":{"name":"peer_review","label":"Peer review"}},{"value":"Single blind","order":1,"name":"review_process","label":"Review process","group":{"name":"peer_review","label":"Peer review"}},{"value":"26 May 2021","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication history"}},{"value":"12 August 2021","order":1,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication history"}},{"value":"7 October 2021","order":2,"name":"published_online","label":"Published online","group":{"name":"publication_history","label":"Publication history"}},{"value":"This article has supporting information","name":"supplementary_materials","label":"Supplementary materials","explanation":{"URL":"https:\/\/scripts.iucr.org\/cgi-bin\/sendsup?hf5424"}},{"value":"\u00a9 Matt S. Queen et al.","order":0,"name":"copyright","label":"Copyright","explanation":{"URL":"http:\/\/journals.iucr.org\/services\/copyrightpolicy.html"},"group":{"name":"copyright_and_licensing","label":"Copyright and licencing"}},{"value":"IUCr licence to publish","order":1,"name":"license","label":"Licence","explanation":{"URL":"https:\/\/journals.iucr.org\/copyright\/licencetopublish.html"},"group":{"name":"copyright_and_licencing","label":"Copyright and licencing"}}]}}