Systematic investigation of the influence of electronic substituents on dinuclear gold(I) amidinates: synthesis, characterisation and photoluminescence studies.

Dinuclear gold(I) compounds are of great interest due to their aurophilic interactions that influence their photophysical properties. Herein, we showcase that gold–gold interactions can be influenced by tuning the electronic properties of the ligands. Therefore, various para substituted (R) N,N′-bis(2,6-dimethylphenyl)formamidinate ligands (pRXylForm; Xyl = 2,6-dimethylphenyl and Form = formamidinate) were treated with Au(tht)Cl (tht = tetrahydrothiophene) to give via salt metathesis the corresponding gold(I) compounds [pRXylForm₂Au₂] (R = –OMe, –Me, –Ph, –H, –SMe, and –CO₂Me). All complexes showed intense luminescence properties at low temperatures. Alignment with the Hammett parameter σ_p revealed the trends in the ¹H and ¹³C NMR spectra. These results showed the influence of the donor–acceptor abilities of different substituents on the ligand system which were confirmed with calculated orbital energies. Photophysical investigations showed their lifetimes in the millisecond range indicating phosphorescence processes and revealed a redshift with the decreasing donor ability of the substituents in the solid state. [ABSTRACT FROM AUTHOR]