Luminescent gold–thallium derivatives with a pyridine-containing 12-membered aza-thioether macrocycle

Abstract

The heterometallic TlI/AuI complex {[Au(C6F5)2Tl]2(L)}n has an unprecedented polymeric structural motif with a metallic pseudo-rhombic Au2Tl2 core that repeats itself to form zig-zag polymers and shows a thermochromic behaviour.

Optical Properties in Heteronuclear Gold(I)/Silver(I) Complexes of Aliphatic Mixed‐Donor Macrocycles Featuring Metallophilic Interactions

“…[4][5][6][7][8][9][10][11][12][13][14][15] Recently, we have considered macrocyclic ligands of different ring size and nature/number of donor atoms to support Au(I)•••M(I) (M = Ag, Tl) metallophillic interactions in the formation of heteronuclear complexes starting from organometallic gold(I) polymeric complexes [{Au(C 6 X 5 ) 2 }M] n (M = Ag(I), Tl(I); X = Cl, F) in low polar solvents (toluene, tetrahydrofuran (THF)). [16][17][18][19][20][21][22][23][24] The results achieved so far clearly proved a great versatility and potentiality of these ligands, in particular, thioether crowns and mixed thia-aza macrocycles also featuring aromatic moieties, in determining unusual structural archetypes, metal ion dispositions and intermolecular Au(I)•••M(I) interaction patterns in the isolated Au(I)/Ag(I) and Au(I)/Tl(I) heteronuclear complexes. However, no external mechanical stimuli-responsive materials were obtained using heteronuclear gold(I) complexes with this type of ligands.…”

Closed-shell d10–d10 mechanochromic [AuPh(CNPh)]n complex: quantum chemistry electronic and optical properties

“…13–21 The self-assembly of molecules with gold atoms involves inter- and intramolecular interactions that lead to the formation of systems with high complexity. 22–30…”

“…[13][14][15][16][17][18][19][20][21] The selfassembly of molecules with gold atoms involves inter-and intramolecular interactions that lead to the formation of systems with high complexity. [22][23][24][25][26][27][28][29][30] This phenomenon is known as "aurophilic interaction". [31][32][33][34][35][36][37][38][39][40][41] These closed-shell interactions are estimated to be energetically similar to hydrogen bonds (7-20 kJ mol −1 ) in the case of gold(I).…”

“…[16][17][18][19][20] The photophysical properties of gold complexes undergo signicant changes when Au-Au interactions are established. [21][22][23][24][25][26] Understanding these systems comes from calculating intermolecular interaction energies and determining how these lead to structures and patterns that result in specic optical properties. Thus, it is possible to rationalize the relationship between the structure and optical properties of gold complexes.…”

Is there a Covalent Au(I)–Au(I) Bond in the trans-(AuX)2 (X = F, Cl, Br, I) Structure? A Post-Hartree–Fock and Density Functional Theory Study

“…This phenomenon is known as metallophilic interaction, and in the particular case that involves gold atoms, it is defined as “aurophilic interaction”. − These closed-shell interactions are estimated to be energetically similar to hydrogen bonds (7–17 kJ/mol) in the case of gold­(I), although these are weaker for silver­(I), copper­(I), platinum­(II), and other metals. − The metallophilic interaction has been determined experimentally via solid-state X-ray diffraction − and NMR/absorption/emission/Raman spectroscopic measurements . From a theoretical point of view, the metallophilic attraction has been understood as the contribution of two terms to the equilibrium distance: dispersion and ionic. − The relativistic effects contribute between 20 and 30% to the energy of interaction for heavy atoms like Pt, Au, Tl, Hg, Pb, and Bi.…”