Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, CanadaT2N 1N4.
Dalton Trans. 2010 Feb 7;39(5):1250-60. doi: 10.1039/b919718d. Epub 2009 Nov 23.
The synthesis and advanced characterization, as well as the complexation behavior of a series of terpyridinyl-ethynyl substituted dithieno[3,2-b:2',3'-d]phospholes is reported. The functionalization of the dithienophosphole core furnishes the system with suitable ligand properties for a variety of transition metal centers (Zn(2+), Ru(2+), Pt(2+)) to form the corresponding complexes. The terpyridinyl-extended ligand systems show pronounced photoluminescence features that are beneficial for the formation of strongly luminescent transition metal complexes potentially to be employed in organic light emitting electrochemical cells. Theoretical calculations support the strong luminescence of the ligands resulting from pi-pi* transitions involving the extended pi-conjugated scaffold. The ligands were found to exhibit remarkable luminescence stability towards protonation, whereas complexation to transition metals shows distinct changes in the photophysical properties that depend of the nature of the transition metal employed.
报告了一系列三吡啶基-乙炔基取代的二噻吩并[3,2-b:2',3'-d]膦的合成、高级表征以及络合行为。二噻吩膦核心的功能化赋予了该系统适合各种过渡金属中心（Zn(2+)、Ru(2+)、Pt(2+)）的合适配体性质，以形成相应的配合物。扩展的三吡啶配体系统显示出明显的光致发光特征，有利于形成强发光过渡金属配合物，有望用于有机发光电化学电池。理论计算支持配体的强发光来自涉及扩展的π共轭支架的π-π*跃迁。发现配体对质子化表现出显著的发光稳定性，而与过渡金属的络合则表现出依赖于所使用的过渡金属的性质的明显的光物理性质变化。
