Zhang Xiao-Peng, Wang Li-Li, Zhang Da-Shuai, Qi Xiao-Wei, Shi Zai-Feng, Lin Qiang
Key Laboratory of Water Pollution Treatment & Resource Reuse of Hainan Province, College of Chemistry and Chemical Engineering, Hainan Normal University Haikou 571158 People's Republic of China
RSC Adv. 2018 Mar 16;8(20):10756-10763. doi: 10.1039/c8ra01330f.
A new pair of adducts comprising one chiral Pt(ii) complex cation, [Pt((-)-L)(Dmpi)] ((-)-1) or [Pt((+)-L)(Dmpi)] ((+)-1) [(-)-L = (-)-4,5-pinene-6'-phenyl-2,2'-bipyridine, (+)-L = (+)-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 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 HO 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.
已获得由一个手性Pt(ii)络合阳离子[Pt((-)-L)(Dmpi)] ((-)-1)或[Pt((+)-L)(Dmpi)] ((+)-1) [(-)-L = (-)-4,5-蒎烯-6'-苯基-2,2'-联吡啶，(+)-L = (+)-4,5-蒎烯-6'-苯基-2,2'-联吡啶，Dmpi = 2,6-二甲基苯基异氰化物]与一个TCNQ˙阴离子组成的一对新加合物，并通过单晶X射线晶体学和红外(IR)光谱对其结构进行了确认。手性Pt(ii)阳离子和TCNQ˙阴离子在甲醇溶液中解离，而在HO溶液中形成电荷转移加合物，导致电子结构受到扰动，手性环境发生改变，紫外可见吸收光谱和电子圆二色光谱的差异证明了这一点。溶剂调节的电荷转移性质也已通过发射光谱和共振光散射光谱得到验证。这些有趣的发现可能在黑色吸收剂和宽带隙半导体的开发中具有潜在应用。
