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Volumn , Issue 11, 2002, Pages 2818-2822

Collapsed molecular rectangles based on rhenium(I) coordination of ethynylpyridyl porphyrins - Synthesis, structure, and bending-induced charge-transfer behavior

Author keywords

Electroabsorption spectroscopy; Molecular rectangles; Porphyrins; Rhenium; Supramolecular chemistry

Indexed keywords

CHARGE TRANSFER; COORDINATION REACTIONS; ELECTRONIC STRUCTURE; GEOMETRY; RHENIUM COMPOUNDS; SUPRAMOLECULAR CHEMISTRY; VAN DER WAALS FORCES;

EID: 0036839952     PISSN: 14341948     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0682(200211)2002:11<2818::AID-EJIC2818>3.0.CO;2-1     Document Type: Article
Times cited : (40)

References (28)
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    • Based on the successful synthesis of molecular squares from alkyl-functionalized dipyridyl porphyrins lacking ethynyl groups (P. J. Stang, J. Fan, Chem. Commun. 1997, 15, 1453-1454; R. V. Slone, J. T. Hupp, Inorg. Chem. 1997, 36, 5422-5423) rectangle construction was initially attempted using the same porphyrins as long edges. Unfortunately, discrete rectangles could not be isolated. In retrospect, the problem almost certainly is steric, stemming from the ca. 90° orientation of the rhenium-coordinating pyridyl functionalities with respect to the porphyrin itself and the subsequent crowding likely accompanying rectangle formation. The elimination of pyridine-proximal alkyl groups and the addition of ethynyl spacers at the 5- and 15-positions permits co-planarization of the porphyrin and appended pyridines and allows for formation of the desired rectangles.
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