Rhenium-based molecular rectangles as frameworks for ligand-centered mixed valency and optical electron transfer

Peter H. Dinolfo, Mary Elizabeth Williams, Charlotte L. Stern, Joseph T. Hupp

Research output: Contribution to journalArticle

173 Citations (Scopus)

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, Hab 2, 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 languageEnglish (US)
Pages (from-to)12989-13001
Number of pages13
JournalJournal of the American Chemical Society
Volume126
Issue number40
DOIs
StatePublished - Oct 13 2004

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Rhenium
Ligands
Electrons
Metals
X ray crystallography
X Ray Crystallography
Carbon Monoxide
Oxidation-Reduction
Metal ions
X-Rays
Ions
X rays
Atoms
Communication

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Rhenium-based molecular rectangles as frameworks for ligand-centered mixed valency and optical electron transfer",
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 {\AA} × 7.2 {\AA} to 5.7 {\AA} × 19.8 {\AA}. 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, Hab 2, 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.",
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Rhenium-based molecular rectangles as frameworks for ligand-centered mixed valency and optical electron transfer. / Dinolfo, Peter H.; Williams, Mary Elizabeth; Stern, Charlotte L.; Hupp, Joseph T.

In: Journal of the American Chemical Society, Vol. 126, No. 40, 13.10.2004, p. 12989-13001.

Research output: Contribution to journalArticle

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