Tetra-rhenium molecular rectangles as organizational motifs for the investigation of ligand-centered mixed valency: Three examples of full delocalization

Peter H. Dinolfo, Joseph T Hupp

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58 Citations (Scopus)

Abstract

Molecular rectangles having the form {[Re(CO)3] 2(X)2}2-μ,μ′-(LL)2, where X is either a bridging alkoxide or phenylthiolate group and LL is 4,4′-bipyridine or pyrazine, are characterized by cofacial LL pairs that are in van der Waals contact across the "long" side of the rectangle. Cyclic voltammetry shows that the redox-accessible bridging ligands, LL, are reduced in sequential, one-electron reactions. The singly reduced rectangles represent an unusual type of mixed-valence compound in which the LL ligands themselves are the redox centers. Spectroelectrochemical measurements for mixed-valence forms of these rectangles reveal intense, asymmetric absorption bands in the near-infrared region, assigned as intervalence transitions. Electroabsorption (Stark spectroscopy) measurements reveal minute changes in dipole moment and therefore a lack of significant charge transfer upon intervalence excitation. Thus, the rectangles are unusual examples of class III (fully valence delocalized) molecular mixed-valence species that employ direct donor-orbital/acceptor-orbital overlap rather than covalent-bond-mediated superexchange to achieve the large electronic coupling strengths required for delocalization.

Original languageEnglish
Pages (from-to)16814-16819
Number of pages6
JournalJournal of the American Chemical Society
Volume126
Issue number51
DOIs
Publication statusPublished - Dec 29 2004

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Rhenium
Oxidation-Reduction
Ligands
Pyrazines
Covalent bonds
Dipole moment
Carbon Monoxide
Cyclic voltammetry
Charge transfer
Absorption spectra
Spectrum Analysis
Spectroscopy
Electrons
Infrared radiation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Tetra-rhenium molecular rectangles as organizational motifs for the investigation of ligand-centered mixed valency: Three examples of full delocalization",
abstract = "Molecular rectangles having the form {[Re(CO)3] 2(X)2}2-μ,μ′-(LL)2, where X is either a bridging alkoxide or phenylthiolate group and LL is 4,4′-bipyridine or pyrazine, are characterized by cofacial LL pairs that are in van der Waals contact across the {"}long{"} side of the rectangle. Cyclic voltammetry shows that the redox-accessible bridging ligands, LL, are reduced in sequential, one-electron reactions. The singly reduced rectangles represent an unusual type of mixed-valence compound in which the LL ligands themselves are the redox centers. Spectroelectrochemical measurements for mixed-valence forms of these rectangles reveal intense, asymmetric absorption bands in the near-infrared region, assigned as intervalence transitions. Electroabsorption (Stark spectroscopy) measurements reveal minute changes in dipole moment and therefore a lack of significant charge transfer upon intervalence excitation. Thus, the rectangles are unusual examples of class III (fully valence delocalized) molecular mixed-valence species that employ direct donor-orbital/acceptor-orbital overlap rather than covalent-bond-mediated superexchange to achieve the large electronic coupling strengths required for delocalization.",
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N2 - Molecular rectangles having the form {[Re(CO)3] 2(X)2}2-μ,μ′-(LL)2, where X is either a bridging alkoxide or phenylthiolate group and LL is 4,4′-bipyridine or pyrazine, are characterized by cofacial LL pairs that are in van der Waals contact across the "long" side of the rectangle. Cyclic voltammetry shows that the redox-accessible bridging ligands, LL, are reduced in sequential, one-electron reactions. The singly reduced rectangles represent an unusual type of mixed-valence compound in which the LL ligands themselves are the redox centers. Spectroelectrochemical measurements for mixed-valence forms of these rectangles reveal intense, asymmetric absorption bands in the near-infrared region, assigned as intervalence transitions. Electroabsorption (Stark spectroscopy) measurements reveal minute changes in dipole moment and therefore a lack of significant charge transfer upon intervalence excitation. Thus, the rectangles are unusual examples of class III (fully valence delocalized) molecular mixed-valence species that employ direct donor-orbital/acceptor-orbital overlap rather than covalent-bond-mediated superexchange to achieve the large electronic coupling strengths required for delocalization.

AB - Molecular rectangles having the form {[Re(CO)3] 2(X)2}2-μ,μ′-(LL)2, where X is either a bridging alkoxide or phenylthiolate group and LL is 4,4′-bipyridine or pyrazine, are characterized by cofacial LL pairs that are in van der Waals contact across the "long" side of the rectangle. Cyclic voltammetry shows that the redox-accessible bridging ligands, LL, are reduced in sequential, one-electron reactions. The singly reduced rectangles represent an unusual type of mixed-valence compound in which the LL ligands themselves are the redox centers. Spectroelectrochemical measurements for mixed-valence forms of these rectangles reveal intense, asymmetric absorption bands in the near-infrared region, assigned as intervalence transitions. Electroabsorption (Stark spectroscopy) measurements reveal minute changes in dipole moment and therefore a lack of significant charge transfer upon intervalence excitation. Thus, the rectangles are unusual examples of class III (fully valence delocalized) molecular mixed-valence species that employ direct donor-orbital/acceptor-orbital overlap rather than covalent-bond-mediated superexchange to achieve the large electronic coupling strengths required for delocalization.

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