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The dinuclear complex [[Tl(eta6-toluene)][Au(C6Cl5)2]] (1) displays very intense blue phosphorescence and a rigidochromic behavior in the solid state. The photophysical measurements in a glassy solution display an oligomerization process via metal-metal interactions. Density functional theory calculations show a distortion of the aurate-thallium T shape in the lowest triplet excited state, leading to a triplet metal-to-metal charge-transfer state.

In this paper, we describe a series of diphenylphosphane and diphenylphosphanide gold(III) and gold(III)/gold(I) complexes containing 3,5-C6Cl2F3 as aryl ligands at gold that have been synthesized due to the arylating and oxidant properties of the new polymeric thallium(III) complex [TlCl(3,5-C6Cl2F3)2]n (1). Its reaction with [Au(3,5-C6Cl2F3)(tht)] (tht = tetrahydrothiophene) produces the gold(III) complex [Au(3,5-C6Cl2F3)3(tht)] (2), which allows the synthesis of the diphenylohosphane derivative [Au(3,5-C6Cl2F3)3(PPh2H)] (3). Its treatment with acetylacetonate gold(I) derivatives leads to two novel AuIII/AuI phosphanido-bridged complexes, [PPN][Au(3,5-C6Cl2F3)3(µ-PPh2)AuCl] (4) and [PPN][{(3,5-C6Cl2F3)3Au(µ-PPh2)}2Au] (5). All these complexes have been characterized, and the crystal structures of 1, 2, 4 and 5 have been established by single crystal X-ray diffraction methods, showing a novel polymeric arrangement in 1. [ABSTRACT FROM AUTHOR]

Abstract: The crystal structure of the polymeric complex [Au5Ag2Tl3(C6F5)10(L1)2]n (L1=1‐aza‐4,10‐dithia‐7‐oxacyclododecane) displays heterotrimetallic Ag⋅⋅⋅Au⋅⋅⋅Tl moieties and is held by unsupported metallophilic interactions. This complex emits at 500 nm in the solid state. Ab initio calculations show that the large thermodynamic stability that helps the formation of this heterotrimetallic system arises from the combination of dispersive forces and a very large dipole moment in the supramolecular arrangement. [ABSTRACT FROM AUTHOR]

Investigates the chemical reaction between gold and thallium (Th) precursors. Synthesis of the gold-heterometal complex; Interaction of the Th atoms with the oxygen atom of an acetone; Linear coordination of the gold centers with pentachlorophenyl groups.

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]

Abstract: The heteropolynuclear complexes [AuTl(C6X5)2] n (X=F, Cl) react with dimethylsulfoxide (DMSO) in different molar ratios leading to products of stoichiometry [Tl2{Au(C6F5)2}2{μ-DMSO}3] n (1), and [Tl2{Au(C6Cl5)2}2{μ-DMSO}2] n (2). These complexes have been structurally characterized and can be viewed as extended linear chains built with Tl–Au–Tl units in which the thallium atoms are bridged by the oxygen atoms of DMSO ligands. Additional [Au(C6X5)2]− fragments interact with one or two thallium centres, respectively, giving rise to two different types of metal–metal interactions in each molecule. Both of them show a strong luminescence in solid state and complex 2 also in solution. The thallium–thallium interaction in this complex is considered to be the responsible of its luminescence, which remains in solution. [Copyright &y& Elsevier]

[AuTl(C6F5)2(en)] (en = ethylenediamine) reacts with cyclic ketones as cyclopentanone (Cy5＝O), cyclohexanone (Cy6＝O) or cycloheptanone (Cy7＝O) in 1:1 or 1:2 molar ratio leading to products of stoichiometry [AuTl(C6F5)2{CyxN(CH2)2NH2}] (x = 5 1, 6 2 or 7 3), or [AuTl(C6F5)2{Cyx＝N(CH2)2N＝Cyx}] (x = 5 4, 6 5 or 7 6). Addition of ethylenediamine to the ketimine complexes in chloroform regenerates [AuTl(C6F5)2(en)], the starting material, and the free ketimines, as their NMR and mass spectra evidenced. The ketimine complexes display luminescence in solid state at room temperature and at 77 K at higher wavelengths than the diamine starting product (505 nm). The excited states responsible for this behaviour are assigned to orbitals due to the gold–thallium interactions. [Copyright &y& Elsevier]

Examines the structure and synthesis of luminescent gold-thallium supramolecular arrays. Effect of donor properties changes in the assembly of atoms; Role of luminescence in the interaction of metal atoms; Nature of orbital involved in metal transitions.