ABAB-type phthalocyanines simultaneously bearing electron donating and electron accepting groups. Synthesis, spectroscopy, and structure

摘要

The ABAB-type 1,4,15,18-tetrapentyloxy-8,11,22,25-tetrachlorophthalocyaninato magnesium compound Mg(trans-TPTCPc) (1) was successfully isolated from the mixed cyclic tetramerization of 4,7-bis(pentyloxy)- 1,3-diiminoisoindoline as precursor A, actually the 1,3-diiminoisoindoline form of 3,6-bis(pentyloxy)- 1,2-benzenedinitrile, and 4,5-dichlorophthalonitrile as precursor B in refluxing pentanol in the presence of magnesium pentoxide in a relatively good yield of 6.2%. Its molecular structure was clearly revealed on the basis of single crystal X-ray diffraction analysis, representing the first structurally characterized ABAB-type phthalocyanine compound, simultaneously bearing electron-donating pentyloxy groups and electron-accepting chloro substituents. Nevertheless, with 1 as the starting material, the corresponding sandwich-type bis(phthalocyaninato) lutetium double-decker complex LuIII(trans- TPTCPc)2 (2) was also prepared and structurally characterized, showing a high hyperpolarizability of 1240 × 10?30 esu as determined by harmonic light scattering (HLS), indicating the great potential of these kinds of phthalocyanine compounds in the field of second-order NLO materials.