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We recently focused on the coordinating ability of the bis(\u03b2\u2010diketonato) ligand bdhb<jats:sup>2\u2212<\/jats:sup>, featuring two \u201cacac\u201d moieties connected through a 1,3\u2010phenylene bridge (H<jats:sub>2<\/jats:sub>bdhb\u00a0=\u00a01,3\u2010bis(3,5\u2010dioxo\u20101\u2010hexyl)benzene). The two crystalline complexes of bdhb<jats:sup>2\u2212<\/jats:sup> so far isolated and structurally characterized, namely [(VO)<jats:sub>2<\/jats:sub>(bdhb)<jats:sub>2<\/jats:sub>] (<jats:bold>1<\/jats:bold>) and [Co<jats:sub>2<\/jats:sub>(bdhb)<jats:sub>2<\/jats:sub>(py)<jats:sub>4<\/jats:sub>] (<jats:bold>2<\/jats:bold>), are dimeric and contain bridging bdhb<jats:sup>2\u2212<\/jats:sup> ligands; however, they become mononuclear and quasi\u2010macrocyclic in organic solution. To investigate this unique structural isomerism by high\u2010resolution <jats:sup>1<\/jats:sup>H NMR spectroscopy, we have now synthesized a diamagnetic Zn<jats:sup>2+<\/jats:sup> analogue of <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold>, namely [Zn<jats:sub>2<\/jats:sub>(bdhb)<jats:sub>2<\/jats:sub>(py)<jats:sub>2<\/jats:sub>] (<jats:bold>3<\/jats:bold>). Although both <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold> are dimeric and contain the same ligands, <jats:bold>3<\/jats:bold> features only one pyridine molecule per metal ion, whose coordination geometry is square pyramidal rather than tetragonally elongated octahedral. The ESI\u2010MS spectra of <jats:bold>3<\/jats:bold> in THF and CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> contain peaks from both monomeric and dimeric species. However, molecular weight determinations by DOSY and conformational studies based on <jats:italic>J<\/jats:italic>\u2010coupling analysis and DFT calculations conclusively prove the rearrangement of <jats:bold>3<\/jats:bold> into quasi\u2010macrocyclic monomers in THF\u2010<jats:italic>d<\/jats:italic><jats:sub>8<\/jats:sub> and CD<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> solution at room temperature.<\/jats:p>","DOI":"10.1002\/chem.202500697","type":"journal-article","created":{"date-parts":[[2025,4,24]],"date-time":"2025-04-24T08:14:33Z","timestamp":1745482473000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Conclusive Insight into the Coordination Complexes of a Flexible Bis(\u03b2\u2010diketonato) Ligand and Their Phase\u2010Dependent Structure: A Multi\u2010Technique Approach"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4963-0025","authenticated-orcid":false,"given":"Manuel","family":"Imperato","sequence":"first","affiliation":[{"name":"Dipartimento di Scienze Chimiche e Geologiche e UdR INSTM Universit\u00e0 degli Studi di Modena e Reggio Emilia  via G. 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Campi 103 Modena 41125 Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4614-1568","authenticated-orcid":false,"given":"Enrico","family":"Benassi","sequence":"additional","affiliation":[{"name":"Department of Natural Sciences Novosibirsk State University  Pirogova St. 1 Novosibirsk 630090 Russia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0288-3233","authenticated-orcid":false,"given":"Nicola","family":"Demitri","sequence":"additional","affiliation":[{"name":"Elettra\u2010Sincrotrone Trieste S.C.p.A.  Basovizza Trieste 34149 Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lara","family":"Gigli","sequence":"additional","affiliation":[{"name":"Elettra\u2010Sincrotrone Trieste S.C.p.A.  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