SYNTHESES, STRUCTURES AND PROPERTIES OF COPPER(1) COORDINATION POLYMERS WITH BRIDGING PHENAZINE - CONSTRUCTION OF ONE-DIMENSIONAL AND 2-DIMENSIONAL STRUCTURES WITH PI-PI STACKING OF PHENAZINE

Four novel copper(I) phenazine (phz) compounds, [{Cu(phz)(NO3)}(infinity)] 1, [{Cu(acr)(2)(NO3)}(2)(phz)-(H2O)] 2 (acr = acridine). [{Cu-2(phz)(PFO3)}(infinity)] 3 and [{[Cu(phz)(MeCN)](2)(C16H10)(PF6)(2)}(infinity)] 4 (C16H10 = pyrene) have been synthesized and their molecular structures and packing have been determined by single-crystal X-ray diffraction methods. The copper atoms in 1 are bridged by phz forming an infinite one-dimensional zigzag chain. These bridging phz molecules have a pi-pi interaction between neighbouring chains forming an infinite columnar stack of phz molecules. The monomer complex, 2, has an infinite columnar stack of metal-free phz and metal-co-ordinated acr. Copper(I) atoms in 3 are bridged by phz and PFO32- alternately. The resulting one-dimensional chains are connected through a tetradentate, asymmetric PFO32- bridge, with pi-pi interaction between the phz molecules forming an infinite two-dimensional sheet structure. The backbone of compound 4 is almost the same as in 1 except that a pyrene molecule is intercalated into every other phz stack in a one-dimensional chain. The electrical conductivity of compound 3 and [{[Cu(phz)(MeCN)](2)(C16H10)(PF6)(2)I-1.3}(infinity)] 5, obtained by iodine doping of compound 4 were 1 x 10(-7.6) and 1 x 10(-4.7) S cm(-1), respectively. The electronic absorption bands of compounds 1, 3 and 4 which appeared around 700 nm are characteristic of copper(I) co-ordination polymers with bridging phz.