2,3,9,10,16,17,23,24-Octakis(hexylsulfonyl)phthalocyanines with good n-type semiconducting properties. Synthesis, spectroscopic, and electrochemical characteristicsElectronic supplementary information (ESI) available: Synthesis procedures for 4,5-di(hexylthio)phthalonitrile, H2Pc(SC6H13)8, Cu[Pc(SC6H13)8], and Zn[Pc(SC6H13)8]; Experimental and simulated isotopic pattern for the molecular ion of Cu[Pc(SO2C6H13)8] (2) shown in the MALDI-TOF mass spectrum; 1H NMR spectra for H2Pc(SC6H13)8, Zn[Pc(SC6H13)8], and H2Pc(SO2C6H13)8(1) in CDCl3; Molecular orbital maps of HOMO and LUMO for MPc and M[Pc(SO2CH3)8] (M = 2H, Zn); the electronic absorption spectra of the aggregates fabricated from 1–3dispersed in methanol; SEM images of the two-electrode device fabricated from the aggregates of 1–3; SEM images and I–Vcurves of the two-electrode devices fabricated from the aggregates of H2Pc(SC6H13)8, Zn[Pc(SC6H13)8], and H2Pc(SO2C6H13)8. See DOI: 10.1039/c1jm10295h

The synthesis of peripherally octa-substituted phthalocyanine compounds with eight strong electron-withdrawing hexylsulfonyl groups was systematically studied. Three new phthalocyanines M[Pc(SO2C6H13)8] [Pc(SO2C6H13)8= 2,3,9,10,16,17,23,24-octakis(hexylsulfonyl)phthalocyaninate; M = 2H (1), Cu (2), Zn (3)] were synthesized viadirect cyclic tetramerization of 4,5-di(hexylsulfonyl)phthalonitrile or through a diiminoisoindoline intermediate. Compounds 1–3could alternatively be prepared by oxidation of the hexylthio substituents in corresponding 2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyanine compounds M[Pc(SC6H13)8] (M = 2H, Cu, Zn) with m-chloroperbenzoic acid. They were fully characterized by elemental analysis and a series of spectroscopic methods. Their electrochemistry was studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Density function theory (DFT) calculations were conducted to study the effect of the strong electron-withdrawing groups on the electronic structure of the phthalocyanine molecules. Particularly, the first reduction potentials in the range −0.30∼−0.04 V vs.the saturated calomel electrode (SCE) for 1–3reveal their n-type semiconducting nature. The current–voltage characteristics of their aggregates demonstrate the good semiconducting properties especially for 1and 2with the conductivity value of 5.24 × 10−4and 2.73 × 10−4S m−1, respectively. [ABSTRACT FROM AUTHOR]