화학공학소재연구정보센터
Inorganic Chemistry, Vol.47, No.3, 1037-1043, 2008
Synthesis, structures, and magnetic properties of metal-coordination polymers with benzenepentacarboxylate linkers
Three hybrid organic-inorganic coordination polymers with benzenepentacarboxylate (BPCA) linkers, [CO3(C6H(COO)5)(OH)(H2O)31 (1-Co), [Zn-3(C6H(COO)(5))(OH)(H2O)(3)] (2-Zn), and [CO5(C6H(COO)(5))(2)(H2O)(12)]center dot(H2O)(12) (3-Co), were synthesized hydrothermally and were characterized structurally and magnetically. 1-Co and 2-Zn are isostructural [C-2/c; Z = 8; 1-Co, a = 19.5350(6) angstrom, b = 10.4494(4) angstrom, and c = 13,2353(5) angstrom, = 97.2768(8)0; 2-Zn, a= 19.5418(g) angstrom, b = 10.3220(10) angstrom, and c = 13.4660(10) angstrom, beta = 98.455(10)degrees] with three-dimensional structures that contain [M-6] secondary building units bridged by BPCA ligands. A different cobalt-based compound, 3-Co, forms at lower pH and lower reaction temperature. Its structure [P2(1/c); Z = 2; a = 12.6162(2) angstrom, b = 11.3768(2) angstrom, and c = 15.3401(3) angstrom, beta = 91.539(1)degrees] is a more loosely packed framework with free (noncoordinated) carboxylic groups pointing at water-filled cavities in the framework. The magnetic phase diagram of 1-Co established through detailed magnetic measurements shows a metamagnetic transition below T-N = 3.8 K. The less-packed compound 3-Co, on the other hand, remains paramagnetic above 1.9 K. The three compounds are the first examples of coordination polymers with benzenepentacarboxylate linkers and fill the gap of coordination polymers involving benzenepolycarboxylate linkers of the general type C6H6-n(COOH)(n), where n = 2-6.