Photoinduced Charge Transfer in Short-Distance Ferrocenylsubphthalocyanine Dyads

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• 作者：Pavlo V. Solntsev ; Katelynn L. Spurgin ; Jared R. Sabin ; Ahmed A. Heikal ; Victor N. Nemykin
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：June 18, 2012
• 年：2012
• 卷：51
• 期：12
• 页码：6537-6547
• 全文大小：632K
• 年卷期：v.51,no.12(June 18, 2012)
• ISSN：1520-510X

文摘

Two new ferrocenylsubphthalocyanine dyads with ferrocenylmethoxide (2) and ferrocenecarboxylate (3) substituents directly attached to the subphthalocyanine ligand via the axial position have been prepared and characterized using NMR, UV鈥搗is, and magnetic circular dichroism (MCD) spectroscopies as well as X-ray crystallography. The redox properties of the ferrocenyl-containing dyads 2 and 3 were investigated using the cyclic voltammetry (CV) approach and compared to those of the parent subphthalocyanine 1. CV data reveal that the first reversible oxidation is ferrocene-centered, while the second oxidation and the first reduction are localized on the subphthalocyanine ligand. The electronic structures and nature of the optical bands observed in the UV鈥搗is and MCD spectra of all target compounds were investigated by a density functional theory polarized continuum model (DFT-PCM) and time-dependent (TD)DFT-PCM approaches. It has been found that in both dyads the highest occupied molecular orbital (HOMO) to HOMO鈥? are ferrocene-centered molecular orbitals, while HOMO鈥? as well as lowest unoccupied molecular orbital (LUMO) and LUMO+1 are localized on the subphthalocyanine ligand. TDDFT-PCM data on complexes 1鈥?b>3 are consistent with the experimental observations, which indicate the dominance of 蟺鈥撓€* transitions in the UV鈥搗is spectra of 1鈥?b>3. The excited-state dynamics of the dyads 2 and 3 were investigated using time-correlated single photon counting, which indicates that fluorescence quenching is more efficient in dyad 3 compared to dyad 2. These fluorescence lifetime measurements were interpreted on the basis of DFT-PCM calculations.