Usuki Tsukasa, Uchida Hikaru, Omoto Kenichiro, Yamanoi Yoshinori, Yamada Ayano, Iwamura Munetaka, Nozaki Koichi, Nishihara Hiroshi
Department of Chemistry, School of Science , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku, Tokyo 113-0033 , Japan.
Graduate School of Science and Engineering , University of Toyama , 3190 Gofuku , Toyama 930-8555 , Japan.
J Org Chem. 2019 Sep 6;84(17):10749-10756. doi: 10.1021/acs.joc.9b01285. Epub 2019 Aug 15.
Ligand functionalization is an attractive strategy for enhancing the performance of metal-based phosphorescent emitters. Here, we report the synthesis and characterization of cyclometalated Pt(II) complexes and containing organosilyl-substituted (2-(2-thienyl)pyridine) ligands and compare their properties with those of (no substituent) and (organocarbon substituent). The photophysical characteristics of these molecules, including their absorption and phosphorescence spectra, phosphorescence quantum yield and lifetime, were investigated. The molecular structures were revealed by X-ray diffraction analysis. Under UV light irradiation, emitted intense orange phosphorescence in the solid state because of the bulkiness of their side chains (up to Φ: 0.49). Optically pure (-)-()- and (+)-()- were prepared using the optically active ligands (+)- and (-)-, respectively. The chiroptical properties of (+)-()-, which has an asymmetric silicon atom, were investigated. Circular dichroism and circularly polarized luminescence measurements showed that these structural motifs are suitable for applications in chiroptical phosphorescent materials.
配体功能化是一种增强金属基磷光发射体性能的有吸引力的策略。在此，我们报告了含有机硅基取代的（2-(2-噻吩基)吡啶）配体的环金属化Pt(II)配合物的合成与表征，并将它们的性质与（无取代基）和（有机碳取代基）的配合物的性质进行比较。研究了这些分子的光物理特性，包括它们的吸收光谱和磷光光谱、磷光量子产率和寿命。通过X射线衍射分析揭示了分子结构。在紫外光照射下，由于其侧链的庞大体积（高达Φ：0.49），在固态中发射出强烈的橙色磷光。分别使用旋光配体(+)-和(-)-制备了光学纯的(-)-()-和(+)-()-。研究了具有不对称硅原子的(+)-()-的手性光学性质。圆二色性和圆偏振发光测量表明，这些结构基序适用于手性光学磷光材料。
