Solvent-tuned charge-transfer properties of chiral Pt(ii) complex and TCNQ˙− anion adducts

Abstract

A new pair of adducts comprising one chiral Pt(II) complex cation, [Pt((−)-L₁)(Dmpi)]⁺ ((−)-1) or [Pt((+)-L₁)(Dmpi)]⁺ ((+)-1) [(−)-L₁ = (−)-4,5-pinene-6′-phenyl-2,2′-bipyridine, (+)-L₁ = (+)-4,5-pinene-6′-phenyl-2,2′-bipyridine, Dmpi = 2,6-dimethylphenylisocyanide], together with one TCNQ˙⁻ anion have been obtained, and the structures have been confirmed via single-crystal X-ray crystallography and infrared (IR) spectroscopy. The chiral Pt(II) cation and TCNQ˙⁻ anion are dissociated in MeOH solution, while charge transfer adducts are formed in H₂O solution, leading to perturbation of the electronic structure and alteration of the chiral environment, as evidenced by the differences in the UV-vis absorption and electronic circular dichroism spectra. The solvent-tuned charge-transfer properties also have been validated through emission and resonance light scattering spectra. The interesting findings may have potential applications in the development of black absorbers and wide band gap semiconductors.