Metalla-supramolecular rectangles as electron reservoirs for multielectron reduction and oxidation

Inorg Chem. 2002 Jul 29;41(15):4025-8. doi: 10.1021/ic020122n.

Abstract

The electron-transfer capacity of molecular rectangle ions [Pt(II)(4)(PEt(3))(8)(mu-anth(2-))(2)(mu-L)(2)](4+) with anth = anthracene-1,8-diyl and L = 4,4'-bipyridine (bp) or 1,2-bis(4-pyridyl)ethene (bpe) was investigated in acetonitrile and dichloromethane using cyclic voltammetry, EPR, and UV-vis-near-IR spectroelectrochemistry. The compounds can be reversibly reduced, first in a two-electron process and then via two closely separated one-electron steps. Oxidation was also possible at rather low potentials in a reversible two-electron step, followed by an electrochemically irreversible process. The spectroscopic results indicate reduction at the neutral acceptor ligands L and oxidation at the formally dianionic anthracene "clips". In contrast, the prototypical molecular square ([Pt(triphos)(mu-bp)](4))(8+) undergoes only irreversible reduction.

Publication types

  • Comparative Study
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Anthracenes / chemistry
  • Electrochemistry
  • Electron Spin Resonance Spectroscopy
  • Ligands
  • Magnetic Resonance Spectroscopy
  • Models, Chemical
  • Molecular Structure
  • Organoplatinum Compounds* / chemical synthesis
  • Organoplatinum Compounds* / chemistry
  • Organoplatinum Compounds* / metabolism
  • Oxidation-Reduction

Substances

  • Anthracenes
  • Ligands
  • Organoplatinum Compounds
  • anthracene