Mixed-ligand coordination polymers from 1,2-bis(1,2,4-triazol-4-yl)ethane and benzene-1,3,5-tricarboxylate: trinuclear nickel or zinc secondary building units for three-dimensional networks with crystal-to-crystal transformation upon dehydration.
The hydrothermal reaction of M(NO3)2.6H2O (M = Ni and Zn) with benzene-1,3,5-tricarboxylic acid (H3btc) and 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) produced the mixed-ligand coordination polymers (MOFs) 3 infinity{[Ni3(mu3-btc)2(mu(4)-btre)2(mu-H2O)2]. approximately 22H2O} (1) and 3 infinity{[Zn3(mu4-btc)2(mu4-btre)(H2O)2].2H2O} (3). The compounds, characterized by single-crystal X-ray diffraction, X-ray powder diffraction and thermoanalysis feature trinuclear secondary building units (SBU) within the three-dimensional frameworks. The trinuclear nickel unit in 1 exhibits an intra-trimer together with some weak inter-trimer antiferromagnetic coupling with J = -13.88(8) cm(-1) from the magnetic susceptibility measurement between 1.9-300 K. The zinc coordination polymer 3 shows a strong fluorescence at 423 nm upon excitation at 323 nm (not seen in the free btre ligand). Compound 3 is thermally robust until 200 degrees C (ambient pressure) where loss of the water molecules starts. Careful control of the dehydration procedure (freeze-drying) for 1 and (heating to 280 degrees C) for allowed for a solid-state reaction with single-crystal-to-single-crystal structural transformations in obtaining the largely dehydrated products 3 infinity{[Ni3(mu2-btc)2(mu4-btre)2(mu-H2O)2(H2O)2].4H2O} (2) and 3 infinity{[Zn3(mu6-btc)2(mu4-btre)2]. approximately 0.67H2O} (4), respectively. In the transformation from 1 to 2 the unit cell volume is reduced to about 60%. The transition from 3 to 4 involves breakage and formation of new Zn-O bonds.
Habib
Hesham A
HA
Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstr. 21, D-79104, Freiburg, Germany.
Sanchiz
Joaquin
J
Janiak
Christoph
C