Tetrameric arrays of the [Re63-Se) 8]2+ clusters supported by a porphyrin core: Synthesis, characterization, and electrochemical studies

Bryan K. Roland, Ware H. Flora, Neal R Armstrong, Zhiping Zheng

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Abstract

A tetracluster array {[Re63-Se)8 (PEt3)5]4 [5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine]}(SbF6) 8 (R4) featuring a central porphyrin core and four circumjacent [Re63-Se)8] 2+ units was synthesized by reacting the previously reported cluster solvate [Re63-Se)8 (PEt3)5(MeCN)](SbF6)2 (R) with 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine. Metallation of R4 with metal (Co2+, Ni2+, Cu2+, Zn2+) salts afforded the corresponding cluster-studded metalloporphyrins (R4-Co, R4-Ni, R4-Cu, and R4-Zn). All compounds were characterized by 1H and 31P NMR spectroscopy and elemental analysis (CHN). Electrochemical studies revealed one chemically reversible oxidation event attributable to the simultaneous removal of four electrons, one from each of the four cluster units. The uncoupled redox event suggests minimal electrical communication between the cluster sites. The cluster arrays were also studied by UV-vis spectroscopy. The electronic spectra of R4-Co, R4 -Ni, and R4-Cu each showed the absorptions of the metalloporphyrins and the cluster complex. For R4-Zn, solvatochromism was observed. Its electronic absorptions in a variety of solvents of different dielectric constants were studied.

Original languageEnglish (US)
Pages (from-to)1798-1807
Number of pages10
JournalComptes Rendus Chimie
Volume8
Issue number11-12
DOIs
Publication statusPublished - Nov 2005

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Keywords

  • Electrochemistry
  • Electronic spectroscopy
  • Metal clusters
  • Porphyrin
  • Rhenium
  • Selenium

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

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