Synthesis and characterization of soluble chloro- and aryl(naphthalocyaninato)indium(III) complexes and their precursors

The syntheses of highly soluble chloro(naphthalocyaninato)indium(III) compo unds (R-2)(4)(R-4)(4)NcInCl (5a: R-2 = H, R-4 = tert-butyl; 6a: R-2 = R-4 = tert-butyl; 7a: R-2 = 2-ethylhexyloxy, R-4 = tert-butyl; 8a: R-2 = R-4 = 2 -ethylhexyloxy), and their reactions with R ' MgBr [b: R ' = p-(trifluorome thyl)phenyl; c; R ' = pentafluorophenyl] producing the axially substituted aryl(naphthalocyaninato)indium(III) compounds 5b, 5c, 6b, 6c, 7b, 7c, 8b, a nd 8c are described. All compounds were characterized by IR, UV/Vis, MS, an d H-1, C-13, and F-19 NMR, as well as by elemental analysis. The high solub ilities of the octasubstituted naphthalocyanines 6-8 and their low tendenci es to form aggregates are due to steric crowding arising from the new unsym metrical peripheral substitution pattern and the bulky, electron-withdrawin g axial ligands. These properties make the (naphthalocyaninato)indium compo unds very interesting candidates for further investigations concerning thei r nonlinear optical properties, particularly for optical limiting applicati ons. We also report on the complete syntheses and characterization of the c orresponding diiminoisoindoline precursors 2 (R-2 = R-4 = tert-butyl), 3 (R -2 = 2-ethylhexyloxy; R-4 = tert-butyl) and 4 (R-2 = R-4 = 2-ethylhexyloxy) .