Novel Multinuclear Cyclic and V-shaped Cuprous Clusters with Short and Unsupported Cu(I)-Cu(I) Separations

A series of novel cyclic and V‐shaped cuprous clusters, (HNEt3)2 [Cu6(bmsapy)4] (1), [Cu8(banlny)4] (2) and [Cu6(ansny)4Cl] (CF3SO3) (3), were synthesized. Compounds (1) and (2) possess a similar cyclic metal structural arrangement, and the metallic arrangement of compound (2) is as in (1) with an insertion of a pair of ligand‐unbridged Cu(I) atoms. Compounds (1) and (2) both have unusual ligand‐unbridged Cu(I)‐Cu(I) separations, but compound (3) does not. The ligand‐unbridged Cu(I)‐Cu(I) distances in (2) are shorter than those in (1). In absorption spectra, compound (2) displayed red shifts from (1) due to the increase in nuclearity and the number of the aromatic rings in ligands. TDDFT calculations suggest that in HOMOs, the major molecular orbital contribution is from the six Cu(I) atoms implying that the photoluminescent property of (1) is dependent on the cyclic hexacopper arrangement rather than that of (HNEt3) [Cu3(btsapy)2] (4). A series of novel cyclic and V‐shaped cuprous clusters, (HNEt3)2 [Cu6(bmsapy)4] (1), [Cu8(banlny)4] (2) and [Cu6(ansny)4Cl] (CF3SO3) (3), were synthesized. Compounds (1) and (2) possess a similar cyclic metal structural arrangement, and the metallic arrangement of compound (2) is as in (1) with an insertion of a pair of ligand‐unbridged Cu(I) atoms. Compounds (1) and (2) both have unusual ligand‐unbridged Cu(I)‐Cu(I) separations. In absorption spectra, compound (2) displayed red shifts from (1) due to the increase in nuclearity and the number of the aromatic rings in ligands