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The coupling between the metal and ligand spins is quantified in terms of the exchange coupling constant (<jats:italic>J<\/jats:italic>) in the platform of density functional theory (DFT) and the wave function\u2010based complete active space self\u2010consistent field (CASSCF) method. Application of DFT and broken symmetry (BS) formalism results ferromagnetic coupling for all the transition metal complexes except the Mn(II) complex. This DFT\u2010BS prediction of magnetic nature matches with the experimental finding for all the complexes other than the Fe(II)\u2010pyDTDA complex, for which an antiferromagnetic coupling between high spin iron and the thiazyl ligand has been reported. However, evaluation of spin state energetics through the multiconfigurational wave function\u2010based method produces the <jats:italic>S=3\/2<\/jats:italic> ground spin state for the iron\u2010thiazyl in parity with experiment. Electronic structure analyses find the overlap between the metal\u2010 and ligand\u2010based singly occupied molecular orbitals (SOMOs) to be one of the major reasons attributing to different extent of exchange coupling in the systems under investigation.<\/jats:p>","DOI":"10.1002\/cphc.202200889","type":"journal-article","created":{"date-parts":[[2023,1,9]],"date-time":"2023-01-09T11:41:07Z","timestamp":1673264467000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["A Theoretical Account of the Coupling between Metal\u2010 and Ligand\u2010centred Spins"],"prefix":"10.1002","volume":"24","author":[{"given":"Sriparna","family":"Roy","sequence":"first","affiliation":[{"name":"Department of Chemistry University of North Bengal  Siliguri Darjeeling\u2009 734013 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6425-0285","authenticated-orcid":false,"given":"Satadal","family":"Paul","sequence":"additional","affiliation":[{"name":"Department of Chemistry Bangabasi Morning College  19 R.C Sarani Kolkata 700009 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9525-1886","authenticated-orcid":false,"given":"Anirban","family":"Misra","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of North Bengal  Siliguri Darjeeling\u2009 734013 India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,1,23]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar00167a004"},{"key":"e_1_2_8_2_1","doi-asserted-by":"crossref","first-page":"6641","DOI":"10.1021\/jp1013835","volume":"114","author":"Misra A.","year":"2010","journal-title":"J. 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