The synthesis and investigation of novel symmetrical phthalocyanines containing 24-membered nitrogen-oxygen mixed donors macrocyclic moieties

SUMMARY l,2-Bis(2-chIoroethoxy)-4,5-dibromobenzene (1) and l,2-bis(2-iyodoetohxy)-4,5- dibromobenzene (2) have been synthesized as premier materials to prepare macrocycle group containing starting ligand which is able to use for preparation of macrocyclic group containing substitue phthalocyanines. (2) has been reacted 6,9-di(toluen-p-sulfonyl)-l,14- di(toluen-p-sulfonylamino)-13,12-dioxa-6,9-diazatetradecane to prepare 25,26-dibromo- 4,10,13,19-tetra(toluen-p-sulfonyl)-l,2,3,4,5,6J,8,9,10,l 1,12,13,14,15,16,17,18,19,20,21, 22,23,24-tetraicosa-hydrobenzo [/] [4, 1 0, 1 3, 1 9]-tetraaza-[ 1, 7, 1 6,22]-tetraoxacyclotetra- icosane (3). Compound (3) has been converted to 25,26-dicyano-4,10,13,19-tetra(toluen-p- sulfonyl)-l,2,3,4,5,6,7,8,9,10,ll,12,13,14,15,16,17,18,19,20,21,22,23,24-tetraicosa-hydro- benzo [/] [4,10,13,19]-tetraaza-[l,7,16,22]-tetraoxacyclotetra-icosane (4) by using CuCN. Tetrakis-macrocyclic-phthalocyaninato Cu(II) (10) has been prepare by tetrameriza- tion of (3) with CuCN. Metal free phthalocyanine derivative (5) has been obtained by self condensation of (4). However (4) has been used to prepare tetrakis-macrocyclic- phthalocyaninato Ni(H) (6), Zn(II) (7), Pb(II) (8) and Co(H) (9) by using related metal salts. The tosyl amid groups of (10) which are in the macrocyclic groups have been hydrolyzed to free amin groups by using concentrated HBr, so tosyl free tetrakis (tetraaza- tetraoxa)-macrocyclic groups containing (11) has been obtained. The aggregation properties in the solutions of (10) and (11) have been investigated as changes on their UV-VIS Spectra. The structures of the compounds have been identified by IR, !H- ve 13C-NMR, UV- VIS, Mass Spectral values and elemental analysis. Key Words : Aggregation, Vibration, Reflux, Macrocyclic, Ligand, Crown Ether, Host-Guest Compound, Rothaxane VII