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Highlights: [•] Complex [{Au(C6Cl5)2}Ag([9]aneS3)]2 displays a [Ag]+–[Au]−–[Au]−–[Ag]+ sequence. [•] Ab initio calculations are used for the study of the nature of the interactions in the Au–Ag complex. [•] Metallophilic Au(I)⋯Ag(I) and C ipso ⋯Ag(I) interactions have an ionic plus a dispersive origin. [•] Au(I)⋯Au(I) and π-stacking interactions mainly arise from dispersive forces. [ABSTRACT FROM AUTHOR]

Abstract: Model compounds are used to study the metallophilic attraction between gold and copper atoms. Ab initio calculations on dimers and tetramers in different distributions of the simplified units are analyzed. An attraction is found for all models and there is a reasonable agreement between the experimental and theoretical geometries. [ABSTRACT FROM AUTHOR]

Structurally similar thiazolyl-hydrazones form complexes of different structures: [Zn 5 (LS1) 4 (AcO) 6 ] (1-AcO) and [Zn(LS3)(AcO)(H 2 O)] (3-AcO). The structure of 1-AcO is unique as it is the first example of a pentanuclear complex with pyridyl-based thiazolyl-hydrazones, containing centrosymmetric Zn 3 (AcO) 6 cluster. Asymmetrical 1-AcO is not photoactive, while 3-AcO displayed photoluminescent emission, attributed to ligand-based transitions. [Display omitted] • Zinc complexes with photophysically inactive thiazolyl-hydrazone (TH) ligands. • 1-AcO is a symmetrical pentanuclear complex with unprecedented Zn 3 (AcO) 6 cluster. • Asymmetrical 3-AcO complex shows emissive properties that arise from IL transitions. • Molecular symmetry impacts photoluminescence in Zn complexes with photoinactive THs. The solid state structures of zinc complexes with HLS1 and HLS3 ligands are reported, where HLS1 is 2-(2-(pyridin-2-ylmethylene)hydrazinyl)-4-fenil-1,3-thiazole and HLS3 is 2-(2-(pyridin-2-ylmethylene)hydrazinyl)-4-(4-methylphenyl)-1,3-thiazole. Structurally similar ligands form complexes of different structures with general formulas [Zn 5 (LS1) 4 (AcO) 6 ] (1-AcO) and [Zn(LS3)(AcO)(H 2 O)] (3-AcO). The pentacoordinated complex 3-AcO exhibits NNN tridentate ligand coordination mode, with additional oxygen donor atoms from a water molecule and acetate anion. The structure of 1-AcO is unique as it is the first example of a pentanuclear complex with pyridyl-based thiazolyl-hydrazone ligands, containing an unprecedented centrosymmetric Zn 3 (AcO) 6 cluster. Photophysical studies showed that 1-AcO is not photoactive, while 3-AcO displayed photoluminescent emission, attributed to ligand-based transitions as determined by time-dependent density functional theory (TD-DFT) calculations. This study underscores the role of molecular symmetry in predicting the photoactivity of at least Zn(II) complexes containing photo-inactive ligands. [ABSTRACT FROM AUTHOR]

Abstract: Model compounds are used to study the metallophilic attraction between gold and thallium atoms. Ab initio calculations on dimers and tetramers in different distributions of the minimal units are analyzed. An attraction is found for all models and there is a reasonable agreement between the experimental and theoretical geometries at the HF and MP2 levels. [Copyright &y& Elsevier]