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Preparation, Structure Determination, and Electrochemical Properties of Bis{[1,4,8,11, 15,18,22,25‐octaethyl‐2,3,9,10,16,17,23,24‐octakis(methylthio)phthalocyaninato]titanium(IV)} Benzene‐1,2,4,5‐tetrathiolate
Author(s) -
Kimura Takeshi,
Kumasaka Jun,
Namauo Toshiharu
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800502
Subject(s) - chemistry , phthalonitrile , phthalocyanine , titanium , electrochemistry , cyclic voltammetry , molecule , proton nmr , inorganic chemistry , benzene , titanium oxide , crystallography , polymer chemistry , electrode , stereochemistry , organic chemistry
4,5‐Bis(methylthio)phthalonitrile 2 was prepared from 2,3,5,6‐tetrabromodiethylbenzene in four steps. Tetramerization and cyclization of phthalonitrile 2 with lithium n ‐pentoxide at 115 °C produced octaethyl‐octakis(methylthio)phthalocyanine ( 3 ). A titanium atom was introduced into thephthalocyanine 3 by treatment with titanium(IV) tetrabutoxide in DMF at 130 °C to give the corresponding metal complex 3‐TiO . Linking of two molecules of the phthalocyanine 3‐TiO with benzene‐1,2,4,5‐tetrathiol ( BTT ) produced a double‐decker‐type compound, bis{[octaethyl‐octakis(methylthio)phthalocyaninato]titanium(IV)} benzenetetrathiolate ( 6 ), in which the two phthalocyanines are connected axially through four titanium–sulfur coordination bonds. Double‐decker derivative 7 was also obtained by a similar treatment of (tetra‐ tert ‐butylphthalocyaninato)titanium(IV) oxide with BTT . The structures of 6 and 7 were determined by NMR, IR, UV/Vis spectroscopy and FAB mass spectrometry. Both phthalocyanine skeletons of 6 have symmetrical structures, as shown by the 1 H and 13 C NMR spectra. The electrochemical properties of 6 were examined by cyclic voltammetry with Ag/AgNO 3 as the reference electrode.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)