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Collapsed Molecular Rectangles Based on Rhenium( I ) Coordination of Ethynylpyridyl Porphyrins − Synthesis, Structure, and Bending‐Induced Charge‐Transfer Behavior
Author(s) -
Benkstein Kurt D.,
Stern Charlotte L.,
Splan Kathryn E.,
Johnson Robert C.,
Walters Keith A.,
Vanhelmont Frederick W. M.,
Hupp Joseph T.
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200211)2002:11<2818::aid-ejic2818>3.0.co;2-1
Subject(s) - porphyrin , chemistry , bent molecular geometry , van der waals force , rhenium , charge (physics) , chemical physics , electronic structure , rectangle , molecular wire , crystallography , photochemistry , computational chemistry , molecule , geometry , inorganic chemistry , organic chemistry , quantum mechanics , physics , mathematics
Efforts to synthesize extremely large rectangle‐shaped porphyrin systems have yielded an unusual and unexpected collapsed structure that brings the porphyrin walls into van der Waals contact. The bent geometry of the nominally rigid ethynylpyridyl porphyrin ligand edges, mandated by the collapse of the rectangle, imparts significant charge‐transfer character to the rectangles' Soret and Q‐region electronic transitions, as shown experimentally by Stark spectroscopy and transient DC photoconductivity measurements, and replicated by electronic structure calculations. In contrast to lower symmetry porphyrin‐like pairs found in naturally occurring photosystems, however, the light‐induced charge transfer is an intra‐porphyrin rather than inter‐porphyrin process. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)