以2,3-二苯基吡嗪或2,3-二苯基喹喔啉为配体的单核和双核金属铂配合物的晶体结构与光物理性质

发布时间：2018-03-16 17:38

本文选题：合成　切入点：单核/双核金属铂氫配合物　出处：《无机化学学报》2017年03期 　论文类型：期刊论文

【摘要】：以2,3-二苯基吡嗪(H_2dpp)、5-甲基-2,3-二苯基吡嗪(H2mdpp)和2,3-二苯基喹喔啉(H_2dpq)为配体,乙酰丙酮(Hacac)为辅助配体,合成了一类单核和双核金属铂配合物[Pt(Hdpp)(acac)](1)、[Pt2(dpp)(acac)2](2)、[Pt(Hmdpp)(acac)](3)和[Pt(Hdpq)(acac)](4),并且得到了配合物2、3和4的晶体结构数据。通过对单核配合物1的类似物配合物3和双核配合物2的配位平面、分子扭曲程度等的晶体结构分析,我们合理地推断以2,3-二苯基吡嗪为配体的双核配合物2具有比相应的单核配合物1更加扭曲的分子平面。通过对配合物1和2的紫外-可见吸收光谱和激发光谱的比较,发现由于双核配合物2在激发态的构型变化造成了激发光谱中最低能带比相应的最低能量吸收带光谱红移了18 nm。因此,尽管双核配合物2具有与单核配合物1类似的紫外-可见吸收光谱,最低能吸收带仅比单核配合物1红移5 nm,但是双核配合物2的最大发射峰值λmax为609 nm,比单核配合物1(λmax=546 nm)红移了63 nm。双核配合物2的发射光谱红移现象与配合物的分子构型直接相关。分子扭曲程度更大的双核配合物2在激发态可能发生了一个向平面性更好的构型转变过程,从而进一步降低了激发态能量,造成了发射光谱的红移。
[Abstract]:The ligands of H2dpp-5- methyl-2-diphenylpyrazine-3-diphenylpyrazine (H2mdppp) and 2-diphenylquinoxaline (H2dpq) were used as the ligands, and acetylacetone (Hacaca) was used as the auxiliary ligands. A class of mononuclear and binuclear metal platinum complexes [PTH Hdppa acaca] 1, [Pt2(dpp)(acac)2] 2 O, [PTT Hmdppa acaca] 3) and [PTT Hdpqqa acaca] 4 are synthesized, and the crystal structure data of complexes 23 and 4 are obtained. The coordination planes of Mononuclear complex 1 analogues 3 and binuclear complexes 2 are obtained. Crystal structure analysis of molecular distortion, etc., We reasonably infer that binuclear complex 2 with 2o 3-diphenyl pyrazine as ligand has a more distorted molecular plane than corresponding mononuclear complex 1. By comparing the UV-Vis absorption spectra and excitation spectra of complexes 1 and 2, It is found that the lowest energy band ratio in the excitation spectrum of binuclear complex 2 redshifts to 18 nm in the corresponding lowest energy absorption band spectrum due to the configuration change of the excited state of binuclear complex 2. Although binuclear complex 2 has a UV-Vis absorption spectrum similar to that of mononuclear complex 1, The lowest energy absorption band is only 5 nm red shift than that of mononuclear complex 1, but the maximum emission peak 位 max of binuclear complex 2 is 609 nm, which redshifts 63 nm compared with that of mononuclear complex 1 (位 max=546 nm). The binuclear complex 2 with greater molecular distortion may undergo a transition to a better planar configuration in the excited state. Thus, the excited state energy is further reduced and the red shift of the emission spectrum is caused.
【作者单位】：四川师范大学化学与材料科学学院;
【基金】：国家自然科学基金(No.21172161,21072147)资助项目
【分类号】：O641.4

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