Selective intercalation of Cs+ in the "V"-shaped cavity of a bichromophoric anion radical: Cs+ assisted pi-s-pi-delocalization of an electron

J Phys Chem A. 2006 Aug 10;110(31):9602-6. doi: 10.1021/jp0624653.

Abstract

EPR studies in tetrahydrofuran, reveal that the one electron reduction of 1-(9-methyl-9H-fluoren-9-yl)-4-methylbenzene via electron transfer from cesium metal produces an anion radical that has a large affinity for the cesium cation. The affinity of this anion radical for Cs+ is so great that it will actually "suck" the Cs+ (but not Na+ or K+) right out of the grasp of 18-crown-6, leading to a cation-assisted pi-stacked complex, where the s-orbital of the metal cation is simultaneously overlapped with the pi-clouds of the phenyl and fluorenyl moieties. At ambient temperature, proton- and cesium-electron coupling constants are rapidly (on the EPR time scale) modulated as a result of the simultaneous existence of two interconverting conformers having an averaged cesium splitting (a(Cs)) of about 1.6 G. The pi-s-pi-electronic coupling can be turned on or off via the addition or removal of cesium cations. Analogous pi-s-pi-electronic coupling is observed in the 1,4-bis(9-methyl-9H-fluoren-9-yl)benzene-cesium system.

Publication types

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

MeSH terms

  • Anions / chemistry*
  • Cesium / chemistry*
  • Computer Simulation
  • Electron Spin Resonance Spectroscopy
  • Electrons*
  • Free Radicals / chemistry
  • Molecular Structure

Substances

  • Anions
  • Free Radicals
  • Cesium