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Synthesis and Nonlinear Optical Absorption of Novel Porphyrin–Osmium‐Cluster Complexes
Author(s) -
Yang Guo Ying,
Ang Siau Gek,
Chng Leng Leng,
Lee Yiew Wang,
Lau Ernest WeiPin,
Lai Kin Seng,
Ang How Ghee
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200390111
Subject(s) - porphyrin , osmium , chemistry , photochemistry , molecule , tetraphenylporphyrin , absorption spectroscopy , cluster (spacecraft) , metal , indium , ruthenium , catalysis , organic chemistry , physics , quantum mechanics , computer science , programming language
Reaction of azido(tetra‐ p ‐tolylporphyrinato)indium( III ) [TTPInN 3 ] and [Os 3 ( μ ‐H) 2 (CO) 10 ] in toluene at 80 °C overnight gave two major products, complexes 1 and 2. Complex 1 had an axial bridge of “NH”, while 2 had an axial bridge of “N” between the porphyrin and osmium cluster moieties. Complex 1 could be converted to 2 when refluxed in toluene. These two novel porphyrin–osmium clusters are the first axially linked porphyrin–metal cluster complexes. UV/Vis spectroscopy revealed the significant ground state electronic perturbation in the capped complex 2 , demonstrating that the remarkable electronic interaction of the moieties within the molecule was achieved by this special structural arrangement. In addition, the electrochemistry of 1 and 2 were investigated and their oxidation current voltage curves are similar to those of indium( III )–porphyrins with a metal–metal σ bond such as [TPPInRe(CO) 5 ] (TPP=tetraphenylporphyrin). The two new molecules also exhibit large nonlinear optical absorption at 532 nm with a ns pulse laser and are potential optical limiting materials for sensor protection in the visible region.