Self-Assembly of Lanthanide Helicate Coordination Polymers into 3D Metal-Organic Framework Structures

Abstract

Pyridine-2,6-dicarboxylic acid (pdcH(2) ) reacts with nitrate salts of La(III), Ce(III), and Nd(III) under hydrothermal conditions to form three-dimensional network structures, 1-4. All the compounds crystallize in the monoclinic space group P2(1)/c with the following lattice parameters: [La(2)(pdc)(3).3H(2)O] 1, a = 10.966(3) A, b = 17.534(4) A, c = 13.578(2) A, beta = 100.23(3) degrees, V( )()= 2569.3(9) A(3), Z = 4, R1 = 0.052, wR2 = 0.143, S = 1.06; [Ce(2)(pdc)(3).3H(2)O] 2, a = 12.701(3) A, b = 9.979(1) A, c = 19.401(4) A, beta = 97.73(2) degrees, V( )()= 2436.6(8) A(3), Z = 4, R1 = 0.039, wR2 = 0.117, S = 1.30; [Ce(2)(pdc)(3).3H(2)O] 3, a = 10.961(5) A, b = 17.523(5) A, c = 13.505(2) A, beta = 100.89(3) degrees, V( )()= 2547.2(8) A(3), Z = 4, R1 = 0.040, wR2 = 0.103, S = 1.08; [Nd(2)(pdc)(3).3H(2)O] 4, a = 10.944(3) A, b = 17.448(5) A, c = 13.397(2) A, beta = 101.19(3) degrees, V( )()= 2569.3(9) A(3), Z = 4, R1 = 0.052, wR2 = 0.143, S = 1.06. Compounds 1, 3, and 4 form infinite single helical chains with large widths and pitches containing four metal ions per turn while 2 forms a different helix with smaller width and pitch containing two metal ions per turn. Each helix is further bonded on either side via carboxylate bridging producing three-dimensional metal-organic framework structures.