Photoluminescence Properties, Molecular Structures, and Theoretical Study of Heteroleptic Silver(I) Complexes Containing Diphosphine Ligands

The homoleptic complex [Ag­(<b>L</b>)₂]­PF₆ (<b>1</b>) and heteroleptic complexes [Ag­(<b>L</b>)­(<b>L</b>_<b>Me</b>)]­BF₄ (<b>2</b>) and [Ag­(<b>L</b>)­(<b>L</b>_<b>Et</b>)]­BF₄ (<b>3</b>) [<b>L</b> = 1,2-bis­(diphenylphosphino)­benzene, <b>L</b>_<b>Me</b> = 1,2-bis­[bis­(2-methylphenyl)­phosphino]­benzene, and <b>L</b>_<b>Et</b> = 1,2-bis­[bis­(2-ethylphenyl)­phosphino]­benzene] were synthesized and characterized. X-ray crystallography demonstrated that <b>1</b>–<b>3</b> possess tetrahedral structures. Photophysical studies and time-dependent density functional theory calculations of <b>1</b>–<b>3</b> revealed that alkyl substituents at the ortho positions of peripheral phenyl groups in the diphosphine ligands have a significant influence on the energy and intensity of phosphorescence of the complex in solution at room temperature. The results can be interpreted in terms of the geometric preferences of each complex in the ground and excited states. The homoleptic complex <b>1</b> exhibits weak orange phosphorescence in solution arising from its flat structure in the triplet state, while heteroleptic complexes <b>2</b> and <b>3</b> show strong green phosphorescence from triplet states with tetrahedral structure. Larger interligand steric interactions in <b>2</b> and <b>3</b> caused by their bulkier ligands probably inhibit geometric relaxation within the excited-state lifetimes, leading to higher energy phosphorescence than that observed for <b>1</b>. NMR experiments revealed that <b>2</b> and <b>3</b> in solution possess structures that are much more immobilized than that of <b>1</b>; fluxional motion is completely suppressed in <b>2</b> and <b>3</b>. Accordingly, conformational changes of <b>2</b> and <b>3</b> are expected to be suppressed by the alkyl substituents not only in the ground state but also in excited states. Consequently, nonradiative decay of the excited states of <b>2</b> and <b>3</b> occurs less efficiently than in <b>1</b>. As a result, the quantum yields of phosphorescence for <b>2</b> and <b>3</b> are 6 times larger than that for the homoleptic complex <b>1