One pot reaction and three type products; 1(4),8(11)-15(18),22(25) adjacent azine attached as macrocyclically mono, bunk-type (dimer) and polymeric metallo phthalocyanines; synthesis, spectroscopy, and electrochemistry

Abstract

In this study, bisdinitriles, 3,3'-(2,2'-(1E,1'E)-hydrazine-1,2-diylidene bis(methan-1-yl-1-ylidene)bis(2,1-phenylene))bis(oxy)diphthalonitrile (1), were prepared using 3-nitro phthalonitrile and 2,2'-(1E,1'E)-hydrazine-1,2-diylidenebis(methan-1-yl-1-ylidene)-diphenol as the starting compounds. Treatment of 1 with corresponding anhydrous metal salts, Zn(acac)(2), CoCl2 and MnCl2 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene gave monomeric (2a, 3a and 4a), bunk-type dimer (2b, 3b and 4b) and polymeric phthalocyanines (2c, 3c and 4c) (MPcs) (M = Zn(II) (2), Co(II) (3), and Mn(III)(4)}. The electron-donating 2,2'-(1E,1'E)-hydrazine-1,2-diylidenebis(methan-1-yl-1-ylidene) diphenol functional units facilitated solubility in polar organic solvents. Upon addition of Ag(I), Na(I), K(I) and Mg(II) ions to the solution of 2 and 3 in THF, only K(I) among them caused profoundly sensing changes in their electronic absorption spectra without shifting, in especial, the Q- and the B-bands of 2a and 3a through the use of hard hard donor-acceptor interactions on the periphery. UV/Vis, FTIR, H-1 NMR, C-13 NMR, MALDI-TOF MS and elemental analysis data were used to characterize the novel compounds in addition to electrochemical characterization. Atomic force microscopy was also used as complementary technique to investigate the morphology of 3a and 3a + K(I). (C) 2014 Elsevier Ltd. All rights reserved.