Abstract
A series of six neutral, tetrametallic, molecular rectangles has been synthesized that have the form ([Re(CO)3]2BiBzlm) 2-μ,μ′(LL)2, where BiBzlm is 2,2′-bisbenzimidazolate and LL is a reducible, dipyridyl or diazine ligand. X-ray crystallographic studies of the six show that the rectangle frameworks, as defined by the metal atoms, range in size from 5.7 Å × 7.2 Å to 5.7 Å × 19.8 Å. The singly reduced rectangles are members of an unusual category of mixed-valence compounds in which the ligands themselves are the redox centers and interligand electronic communication is controlled by direct ligand orbital overlap rather than by superexchange through the metal ions. Despite nominally identical coordination-defined ligand positioning, the spectrally determined electronic strengths, Hab2, vary by roughly 100-fold. As shown by X-ray crystallography and computational modeling, the observed differences largely reflect detailed geometric configurational differences that can either facilitate or frustrate productive direct orbital overlap.
Original language | English (US) |
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Pages (from-to) | 12989-13001 |
Number of pages | 13 |
Journal | Journal of the American Chemical Society |
Volume | 126 |
Issue number | 40 |
DOIs | |
State | Published - Oct 13 2004 |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry
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CCDC 253341: Experimental Crystal Structure Determination
Dinolfo, P. H. (Creator), Williams, M. E. (Creator), Stern, C. L. (Creator) & Hupp, J. T. (Creator), Cambridge Crystallographic Data Centre, 2005
DOI: 10.5517/cc8hm9n, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc8hm9n&sid=DataCite
Dataset
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CCDC 253339: Experimental Crystal Structure Determination
Dinolfo, P. H. (Creator), Williams, M. E. (Creator), Stern, C. L. (Creator) & Hupp, J. T. (Creator), Cambridge Crystallographic Data Centre, 2005
DOI: 10.5517/cc8hm7l, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc8hm7l&sid=DataCite
Dataset
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CCDC 253340: Experimental Crystal Structure Determination
Dinolfo, P. H. (Creator), Williams, M. E. (Creator), Stern, C. L. (Creator) & Hupp, J. T. (Creator), Cambridge Crystallographic Data Centre, 2005
DOI: 10.5517/cc8hm8m, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc8hm8m&sid=DataCite
Dataset