Studies On Metal Complexes Based On The Dihydrazonato Ligands Bearing Pyridine-2, 6-dicarboxylic Acid And 1, 1'-Ferrocene Dicarboxylic Acid

Coordination polymers and multinuclear complexes have attracted much attention because of both fascinating structures and potential applications in functional materials and so on. Six novel coordination compounds are synthesized by using bis[(3-methoxysalicylidene)-2,6- dihydrazonatoyl]pyridine(BMSPD),bis[(3-carboxysalicylidene)-2,6-dihydrazonatoyl]pyridine (BCSPD) and Bis(3-methoxysalicylidene)-(ferrocene-1,1-diyldicarbonyl)dihydrazonato (BMS FD) as ligands. The complexes are characterized by IR,elemental analysis and single crystal X-ray diffraction.Thermogravimetric analysis (TGA) and luminescent properties of some com-plexes have been studied. Works are listed as follow:1.Three new multinuclear complexes [Cu6(BMSPD)2(S2O8)2(H2O)6]·4H2O (1),[Cu3(BMSPD)(ClO4)2(H2O)4]·5H2O(2),[Cu3(BMSPD)(DMF)4(H2O)2]·H2O·2DMF·2ClO4 (3) have been synthesized with copper salts and BMSPD and characterized by elemental analysis, Infrared (IR) spectroscopy,and single crystal X-ray diffraction.The thermogravimetric analysis for complex (2) has been stuided as well.It was shown that complex (1) crystallizes in the tri-clinic system, space group P1, with a =10.1795(8)?, b =13.9093(14)?, c =14.5460(17)?,β=75.989(3)°;Complex (2) crystallizes in the triclinic system, space group P 1 , with a =10.5593(13)?, b =11.1133(14)?, c =17.129(2)?,β=87.596(2)°; Complex (3) crystallizes in the triclinic system, space group P 1 , with a =14.6377(13)?, b =14.7695(14)?, c =16.1666(18)?,β=66.6160(10)°. In the hexauclear complex (1), Cu(II) is five-coordinated in a distorted tetragonal pyramid geometry. The coordination atoms with Cu(1) are three N atoms from BMSPD and two O atoms from H2O. The coordination atoms with Cu(2) are one N atom from BMSPD and four O atoms. The coordination atoms with Cu(3) are one N atom and two O atoms from BMSPD and two O atoms from H2O. The O atom from peroxodisulfate anion (S2O82–) adopts aμ1,3-O bridging coordination mode,bridging two trinuclear Cu(II) units to form a hexanuclear structure. In the complex (2), Cu(1) is five-coordinated in a distorted trigonal bipyramid(τ=0.38) geometry, the coordination atoms are three N atoms and two O atoms . Cu(2) is five-coordinated in a distorted tetragonal pyramid(τ=0.0648) geometry. The coordination at-oms with Cu(2) are one N atom from BMSPD and four O atoms. Cu(3) is five-coordinated in a distorted tetragonal pyramid(τ=0.0155) geometry. The coordination atoms with Cu(3) are one N atom from BMSPD and four O atoms. In the complex (3), Cu(1) is five-coordinated in a dis-torted trigonal bipyramid(τ=0.36) geometry, the coordination atoms are three N atoms from BMSPD and two O atoms from H2O. Cu(2) is five-coordinated in a distorted tetragonal pyra-mid(τ=0.0438) geometry, Cu(3) is five-coordinated with distorted tetragonal pyramid(τ=0.0377) geometry.2.A new coordination polymer {[Zn5(BMSPD)(OAc)5Cl(H2O)3]·2H2O}n (4) has been synthesized with the ligand BMSPD and characterized by elemental analysis, Infrared (IR) spec-troscopy,thermogravimetric analysis and single crystal X-ray diffraction. The luminescent property of the complex has been studied as well. Complex (4) crystallizes in the monoclinic system, space group P21/n, with a=10.0544(14)?, b=14.357(2)?, c=32.342(3)?,β= 98.236(2)°.There are three kinds of coordination geometries of Zn(II) ions in the complex (4), Zn(1) is five-coordinated in a distorted tetragonal pyramid geometry, Zn(2) is five-coordinated in a distorted trigonal bipyramid geometry,the coordination atoms are one N atom from BMSPD and four O atoms. Zn(3) is six-coordinated in a distorted octahedronal geometry, Zn(4) is five-coordinated with distorted trigonal bipyramid, Zn(5) is six-coordinated with distorted octa-hedronal geometry, the coordination atoms are six O atoms . 3. One trinuclear complex [Cu3(BCSPD)2(ClO4)2(H2O)4]·3H2O(5) has been synthesized with the ligand BCSPD and characterized by elemental analysis, Infrared (IR) spectroscopy and single crystal X-ray diffraction. It was shown that complex (5) crystallizes in the triclinic system, space group P1, with a =9.8385(10)?, b =11.4596(13)?, c =18.790(2)?,β=78.212(2)°.4.One dodecanuclear complex [Ni12(BMSFD)4(OAc)8(H2O)12 (CH3OH)4]·8H2O·5CH3OH(6) has been synthesized with the ligand BMSFD and characterized by elemental analysis, Infrared (IR) spectrosco py and single crystal X-ray diffraction. It was shown that complex (6) crystal-lizes in the monoclinic system, space group P2/n, with a =22.570(3)?, b =11.9935 (16)?, c =38.198(3)?,β=98.801(2)°.The complex possesses a ferrocene-containing macrocyclic.