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Two homologous MOFs [Co<jats:sub>2<\/jats:sub>(NDC)<jats:sub>2<\/jats:sub>(DPTTZ)<jats:sub>2<\/jats:sub>]. DPTTZ. DMF, <jats:bold>1<\/jats:bold> and [Co<jats:sub>2<\/jats:sub>(BDC)<jats:sub>2<\/jats:sub>(DPTTZ)<jats:sub>2<\/jats:sub>]. DMF, <jats:bold>2<\/jats:bold> (where NDC=naphthalene dicarboxylate, BDC=benzene dicarboxylate, DPTTZ=<jats:italic>N, N<\/jats:italic>\u2032\u2010di(4\u2010pyridyl)thiazolo\u2010[5,4\u2010d]thiazole, DMF=<jats:italic>N, N<\/jats:italic>\u2032\u2010dimethyl formamide) are considered for this, whose intra\u2010dimer distance of redox\u2010active DPTTZ ligands differs ca. 1\u2005\u00c5 from one system to another. Spectroelectrochemical study detects the formation of IVCT band at the NIR region between cofacially oriented DPTTZ molecules in both MOFs. Transient spectroscopy shows faster charge separation as well as charge recombination when intra\u2010dimer distance is lesser (in MOF <jats:bold>2<\/jats:bold>) due to stronger electronic coupling. We quantify the extent of IVCT by charge transfer integral calculation; and also by optical pump terahertz probe spectroscopy, where MOF <jats:bold>2<\/jats:bold> shows three times higher carrier mobility due to lesser inter\u2010DPTTZ distance than MOF <jats:bold>1<\/jats:bold>. These findings reveal a more localized aspect of through\u2010space IVCT between cofacially organized redox\u2010active pair in a three\u2010dimensional framework.<\/jats:p>","DOI":"10.1002\/anie.202308034","type":"journal-article","created":{"date-parts":[[2023,6,19]],"date-time":"2023-06-19T02:24:28Z","timestamp":1687141468000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Influence of Molecular Separation on Through\u2010Space Intervalence Transient Charge Transfer in Metal\u2013Organic Frameworks with Cofacially arranged Redox Pairs"],"prefix":"10.1002","volume":"62","author":[{"given":"Akashdeep","family":"Nath","sequence":"first","affiliation":[{"name":"School of Chemistry Indian Institute of Science Education and Research Thiruvananthapuram  Kerala 695551 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Vikas","family":"Kumar","sequence":"additional","affiliation":[{"name":"Institute of Nano Science and Technology  Sector-81, Knowledge City Sahibzada Ajit Singh Nagar Punjab Pin - 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