本文選題：合成　切入點(diǎn)：單核/雙核金屬鉑氫配合物　出處：《無機(jī)化學(xué)學(xué)報(bào)》2017年03期 　論文類型：期刊論文

【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)為配體,乙酰丙酮(Hacac)為輔助配體,合成了一類單核和雙核金屬鉑配合物[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的晶體結(jié)構(gòu)數(shù)據(jù)。通過對(duì)單核配合物1的類似物配合物3和雙核配合物2的配位平面、分子扭曲程度等的晶體結(jié)構(gòu)分析,我們合理地推斷以2,3-二苯基吡嗪為配體的雙核配合物2具有比相應(yīng)的單核配合物1更加扭曲的分子平面。通過對(duì)配合物1和2的紫外-可見吸收光譜和激發(fā)光譜的比較,發(fā)現(xiàn)由于雙核配合物2在激發(fā)態(tài)的構(gòu)型變化造成了激發(fā)光譜中最低能帶比相應(yīng)的最低能量吸收帶光譜紅移了18 nm。因此,盡管雙核配合物2具有與單核配合物1類似的紫外-可見吸收光譜,最低能吸收帶僅比單核配合物1紅移5 nm,但是雙核配合物2的最大發(fā)射峰值λmax為609 nm,比單核配合物1(λmax=546 nm)紅移了63 nm。雙核配合物2的發(fā)射光譜紅移現(xiàn)象與配合物的分子構(gòu)型直接相關(guān)。分子扭曲程度更大的雙核配合物2在激發(fā)態(tài)可能發(fā)生了一個(gè)向平面性更好的構(gòu)型轉(zhuǎn)變過程,從而進(jìn)一步降低了激發(fā)態(tài)能量,造成了發(fā)射光譜的紅移。
[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.
【作者單位】： 四川師范大學(xué)化學(xué)與材料科學(xué)學(xué)院;
【基金】：國(guó)家自然科學(xué)基金(No.21172161,21072147)資助項(xiàng)目
【分類號(hào)】：O641.4

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