Abstract
3,6‐Diethylphthalonitrile (3) with a tetrathiafulvalene (TTF) unit at 4,5‐positions was prepared from 4,5‐xylylenedithio‐3,6‐diethylphthalonitrile (1a) via elimination of the xylylene group, connection of a carbonyl group to benzenedithiolate generated, and condensation of 4,5‐bis(methylthio)‐1,3‐dithiole‐2‐thione with benzo‐1,3‐dithiole‐2‐one (2‐O) produced. A 1:1 mixture of phthalonitrile (3) and 4,5‐bis(benzylthio)‐3,6‐diethylphthalonitrile (1b) was treated with lithium in n‐hexanol at 120°C to produce hexakis (benzylthio)mono(tetrathiafulvaleno)phthalocyanine (5), tetrakis(benzylthio)bis(tetrathiafulvaleno)phthalocyanine (6), and bis(benzylthio)tris(tetrathiafulvaleno)phthalocyanine (7). The structures of 5, 6, and 7 were determined by ^1^H NMR, FAB MS, MALDI‐TOF MS (matrix assisted laser desorption ionization time‐of‐flight mass spectrometry), and UV‐‐vis spectroscopy. Compound 6 is a mixture of trans and cis isomers (6‐trans and **6‐**cis). The UV‐‐vis spectrum of 5 measured in chloroform changed by addition of trifluoroacetic acid (TFA). The Q band absorption at λ~max~ = 755 nm (chloroform) decreased in intensity and resulted in a new absorption at λ~max~ = 740 nm (chloroform/TFA). The electrochemical properties of 5, 6, and 7 were determined by cyclic voltammetry using Ag/AgNO~3~ as a reference electrode. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:605–611, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20694