title: Linkage dependence of intramolecular fluorescence quenching process in porphyrin-appended mixed (phthalocyaninato)(porphyrinato) yttrium(III) double-decker complexes.
abstract: Three novel mixed (phthalocyaninato)(porphyrinato) yttrium double-decker complexes appended with one metal-free porphyrin chromophore at the para, meta, and ortho position, respectively, of one meso-phenyl group of the porphyrin ligand in the double-decker unit through ester linkage, 3-5, have been designed, synthesized, and spectroscopically characterized. The photophysical properties of these three isomeric tetrapyrrole triads were comparatively investigated along with the model compounds metal-free tetrakis(4-butyl)porphyrin H(2)TBPP (1) and mixed [1,4,8,11,15,18,22,25-octakis(butyloxyl)phthalocyaninato][tetrakis(4-butyl)porphyrinato] yttrium double-decker complex HY[Pc(α-OC(4)H(9))(8)](TBPP) (2) by steady-state and transient spectroscopic methods. The fluorescence of the metal-free porphyrin moiety attached through ester linkage at the meta and ortho position of one meso-phenyl group of porphyrin ligand in the double-decker unit in triads 4 and 5 is effectively quenched by the double-decker unit, which takes place in several hundred femtoseconds. However, the fluorescence of the metal-free porphyrin moiety attached at the para position of one meso-phenyl group of porphyrin ligand in the double-decker unit in triad 3 is only partially quenched, clearly revealing the effect of the position of porphyrin-substituent on the photophysical properties of the triads. Furthermore, the molecular structures of 3-5 were simulated using density functional theory calculations. It was found that the relative orientation between the metal-free porphyrin moiety and the double-decker unit for compound 3 is crossed, while those for compounds 4 and 5 are open- and closed-shellfish-like, respectively, which is suggested to be responsible for their different intramolecular fluorescent quenching efficiency.
authors.affiliation: Department of Chemistry, Shandong University, Jinan 250100, China.
authors.forename: Xianyao
authors.initials: X
authors.lastname: Zhang
authors.forename: Yong
authors.initials: Y
authors.lastname: Li
authors.forename: Dongdong
authors.initials: D
authors.lastname: Qi
authors.forename: Jianzhuang
authors.initials: J
authors.lastname: Jiang
authors.forename: Xingzhong
authors.initials: X
authors.lastname: Yan
authors.forename: Yongzhong
authors.initials: Y
authors.lastname: Bian