Electroswitchable photoluminescence activity: Synthesis, spectroscopy, electrochemistry, photophysics, and X-ray crystal and electronic structures of[Re(bpy)(CO)3(C≡C-C6H4-C≡C)Fe(C5Me5)(dppe)][PF6]n (n = 0, 1)
Electroswitchable photoluminescence activity: Synthesis, spectroscopy, electrochemistry, photophysics, and X-ray crystal and electronic structures of[Re(bpy)(CO)3(C≡C-C6H4-C≡C)Fe(C5Me5)(dppe)][PF6]n (n = 0, 1)
复制标题
DOI：
10.1021/ic030226d
复制
发表时间：
2003-10
影响因子：
4.6
通讯作者：
K. M. Wong;Sally Chan-Fung Lam;C. Ko;N. Zhu;V. Yam;S. Roué;C. Lapinte;S. Fathallah;K. Costuas;S. Kahlal;J. Halet
中科院分区：
文献类型：
--
作者：
K. M. Wong;Sally Chan-Fung Lam;C. Ko;N. Zhu;V. Yam;S. Roué;C. Lapinte;S. Fathallah;K. Costuas;S. Kahlal;J. Halet
合成了一种新的杂环炔基桥联配合物[Re（bpy）（CO）3（C <$CC6H4C <$C）Fe（C5 Me 5）（dppe）]，1及其氧化产物[Re（bpy）（CO）3（C <$CC6H4C <$C）Fe（C5 Me 5）（dppe）][PF 6]，2，并测定了它们的晶体结构.还合成并表征了相关的亚乙烯基配合物[Re（bpy）（CO）3（C = CC 6 H4（H）CC）Fe（C5 Me 5）（dppe）][PF 6]，3。1的循环伏安图显示在-1.49 V（vs SCE）处的准可逆还原对，在-0.19 V处的完全可逆氧化，和在+0.88 V处的准可逆氧化。与电化学结果雅阁的是，氢取代的模型配合物Re（bpy）（CO）3的密度泛函理论计算（C <$CC6H4C <$C）Fe（C5 H5）（dHpe）（Cp = C5 H5，dHpe = H2 P（CH 2）2 PH 2）（1-H）表明LUMO主要是联吡啶配体π* 的特征，而HOMO主要是铁（II）d轨道的特征.化合物1在二氯甲烷中的电子吸收光谱在390 nm处有一个420 nm的肩峰，而化合物2的电子吸收光谱在390 nm处有一个420 nm的肩峰。
A novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO)3(C⋮CC6H4C⋮C)Fe(C5Me5)(dppe)], 1, and its oxidized species, [Re(bpy)(CO)3(C⋮CC6H4C⋮C)Fe(C5Me5)(dppe)][PF6], 2, have been synthesized and their X-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO)3(C⋮CC6H4(H)CC)Fe(C5Me5)(dppe)][PF6], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows a quasireversible reduction couple at −1.49 V (vs SCE), a fully reversible oxidation at −0.19 V, and a quasireversible oxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen-substituted model complex Re(bpy)(CO)3(C⋮CC6H4C⋮C)Fe(C5H5)(dHpe) (Cp = C5H5, dHpe = H2P(CH2)2PH2) (1-H) show that the LUMO is mainly bipyridine ligand π* in character while the HOMO is largely iron(II) d orbital in character. The electronic absorption spectrum of 1 shows low-energy absorption at 390 nm with a 420 nm shoulder in CH2Cl2, while that of 2 exhibits less intense...