Electroswitchable Photoluminescence Activity: Synthesis, Spectroscopy, Electrochemistry, Photophysics, and X-ray Crystal and Electronic Structures of [Re(bpy)(CO)3(C
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- 作者：Keith Man-Chung Wong ; Sally Chan-Fung Lam ; Chi-Chiu Ko ; Nianyong Zhu ; Vivian Wing-Wah Yam ; Sé ; verine Roué ; Claude Lapinte ; Sofiane Fathallah ; Karine Costuas ; Samia Kahlal ; and Jean-Fran
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：November 3, 2003
- 年：2003
- 卷：42
- 期：22
- 页码：7086 - 7097
- 全文大小：230K
- 年卷期：v.42,no.22(November 3, 2003)
- ISSN：1520-510X
文摘
A novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO)3(C
C-C6H4-CC)Fe(C5Me5)(dppe)], 1, and itsoxidized species, [Re(bpy)(CO)3(CC-C6H4-CC)Fe(C5Me5)(dppe)][PF6], 2, have been synthesized and theirX-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO)3(CC-C6H4-(H)C=C)Fe(C5Me5)(dppe)][PF6], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows aquasireversible reduction couple at -1.49 V (vs SCE), a fully reversible oxidation at -0.19 V, and a quasireversibleoxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen-substituted model complex Re(bpy)(CO)3(CC-C6H4-CC)Fe(C5H5)(dHpe) (Cp = C5H5, dHpe = H2P-(CH2)2-PH2) (1-H) show that the LUMO is mainly bipyridine ligand 
* 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 a420 nm shoulder in CH2Cl2, while that of 2 exhibits less intense low-energy bands at 432 and 474 nm and additionallow-energy bands in the NIR at ca. 830, 1389, and 1773 nm. Unlike the related luminescent rhenium(I)-alkynylcomplex [Re(bpy)(CO)3(CC-C6H4-CC-H)], 4, complex 1 is found to be nonemissive, and such a phenomenonis attributed to an intramolecular quenching of the emissive d(Re) 
*(bpy) 3MLCT state by the low-lying MLCTand LF excited states of the iron moiety. Interestingly, switching on of the luminescence property derived from thed(Re) *(bpy) 3MLCT state can be demonstrated in the oxidized species 2 and the related vinylidene analogue3 due to the absence of the quenching pathway.
C-C6H4-CC)Fe(C5Me5)(dppe)], 1, and itsoxidized species, [Re(bpy)(CO)3(CC-C6H4-CC)Fe(C5Me5)(dppe)][PF6], 2, have been synthesized and theirX-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO)3(CC-C6H4-(H)C=C)Fe(C5Me5)(dppe)][PF6], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows aquasireversible reduction couple at -1.49 V (vs SCE), a fully reversible oxidation at -0.19 V, and a quasireversibleoxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen-substituted model complex Re(bpy)(CO)3(CC-C6H4-CC)Fe(C5H5)(dHpe) (Cp = C5H5, dHpe = H2P-(CH2)2-PH2) (1-H) show that the LUMO is mainly bipyridine ligand * 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 a420 nm shoulder in CH2Cl2, while that of 2 exhibits less intense low-energy bands at 432 and 474 nm and additionallow-energy bands in the NIR at ca. 830, 1389, and 1773 nm. Unlike the related luminescent rhenium(I)-alkynylcomplex [Re(bpy)(CO)3(CC-C6H4-CC-H)], 4, complex 1 is found to be nonemissive, and such a phenomenonis attributed to an intramolecular quenching of the emissive d(Re) *(bpy) 3MLCT state by the low-lying MLCTand LF excited states of the iron moiety. Interestingly, switching on of the luminescence property derived from thed(Re) *(bpy) 3MLCT state can be demonstrated in the oxidized species 2 and the related vinylidene analogue3 due to the absence of the quenching pathway.