Preparation and Optical and Electrochemical Properties of Boron (III) Octafluorosubphthalocyanines with One Triselenole and One Diselenet Ring.

Abstract

Unsymmetric boron (III) subphthalocyanines with a triselenole ring or a diselenete ring and eight fluoro groups were prepared by the reaction of 5,6-dicyano-4,7-diethylbenzo-[1,2,3]triselenole and tetrafluorophthalonitrile with trichloroborane in xylene. The reaction was accompanied by a contraction of the triselenole ring to the diselenete ring. The substrate, dicyanobenzo[1,2,3]triselenole, was prepared by a new procedure via a photolytic demethylenation reaction of 3,7-diethyl[1,3]diselenolophthalonitrile using a 10 W white LED light. While triselenolosubphthalocyanine was treated by triphenylphosphine to give the diselenete derivative, the reaction of diselenetosubphthalocyanine with Woolion's reagent produced the expanded triselenole ring. The diselenete derivative reacted with tetrakis(triphenylphosphine)platinum to yield the corresponding platinum complex with Se-Pt bonds. Q-band absorption for the products appeared at around λmax=590 nm in the UV-vis spectrum and weak emission was observed at about λe=620 nm. When diselenetosubphthalocyanine was treated with pentachloro antimonate in dichloromethane or sodium metal in hexane/tetrahydrofuran, the solution showed strong ESR signals. The structures of model compounds were optimized using the DFT method with the Gaussian 09 program at the B3LYP/6-31G (d, p) level.