Tetrakis(diethyl‐phosphonat)‐, Tetrakis(ethyl‐phenylphosphinat)‐ und Tetrakis(diphenylphosphin‐oxid)‐substituierte Phthalocyanine

Abstract

AbstractTetrakis(diethyl phosphonate), Tetrakis(ethyl phenylphosphinate)‐, and Tetrakis(diphenylphosphine oxide)‐Substituted PhthalocyaninesThe title compounds 7, 9, and 11 are obtained by tetramerization of diethyl (3,4‐dicyanophenyl)phosphonate (5), ethyl (3,4‐dicyanophenyl)phenylphosphinate (8), and 4‐(diphenylphosphinyl)benzene‐1,2‐dicarbonitrile (10). The 31P‐NMR spectra of the phthalocyanines 7, 9, and 11 and of their metal complexes present five to eight signals confirming the formation of four constitutional isomers with the expected C4h, D2h, C2v, and Cs symmetry. In the FAB‐MS of the Zn, Cu, and Ni complexes of 7 and 9, the peaks of dimeric phthalocyanines are observed. By gel‐permeation chromatography, the monomeric complex [Ni(7)] and a dimer [Ni(7)]2 can be separated. These dimers differ from the known phthalocyanine dimers, i.e., possibly the P(O)(OEt)2 and P(O)(Ph)(OEt) substituents in 7 and 9 are involved in complexation. The free phosphonic acid complex [Zn(12)] and [Cu(12)] are H2O‐soluble. In the FAB‐MS of [Zn(12)], only the peaks of the dimer are present; the ESI‐MS confirms the existence of the dimer and the metal‐free dimer. In the UV/VIS spectrum of [Zn(12)], the hypsochromic shift characteristic for the known type of dimers from 660–700 nm to 620–640 nm is observed. As in the FAB‐MS of [Zn(12)], the free phosphinic acid complex [Zn(13)] shows only the monomer, an ESI‐MS cannot be obtained for solubility problems. The UV/VIS spectrum of [Zn(13)] demonstrates the existence of the monomer as well as of the dimer.