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论文类型：期刊论文

发表时间：2010-06-20

发表刊物：INORGANICA CHIMICA ACTA

收录刊物：SCIE

卷号：363

期号：10

页面范围：2185-2192

ISSN号：0020-1693

关键字：Hybrid complexes; Porphyrin; Polyoxometalate; Paramagnetic H-1 NMR; Steady-state and time-resolved luminescence

摘要：New complexes based on a coordination interaction between a pyridyl-porphyrin (namely 5,10,15-tritolyl-20-(4-pyridyl)porphyrin, 5,10,15-tritolyl-20-(3-pyridyl)porphyrin or 5,10,15-triphenyl-20-(4-pyridyl)porphyrin) and a Keggin-type polyoxometalate (alpha-[MSiW11O39](6-), M=Co2+ or Ni2+) are formed in solution. The formation of these complexes is clearly evidenced by steady-state and time-resolved luminescence measurements. A strong quenching of the porphyrin fluorescence, accompanied by an important shortening of the fluorescence lifetime, is observed upon addition of the POM and formation of the complexes. Using a variant of the Job's method from the luminescence spectra, the association constants of the complexes have been estimated to be around 10(6) L mol(-1). Paramagnetic H-1 NMR experiments confirm the formation of the complexes. Indeed, in addition to broadenings of the signals, the coordination binding of the POM to the porphyrin induces large high-frequency shifts for the protons of the pyridyl group coordinated to the paramagnetic metal, and low-frequency shifts for all the other resonances. (C) 2010 Elsevier B.V. All rights reserved.