Hydrothermal assembly, structures, topologies, luminescence, and magnetism of a novel series of coordination polymers driven by a trifunctional nicotinic acid building block

作者：Gu, Jin-Zhong^*; Liang, Xiao-Xiao; Cai, Yan; Wu, Jiang; Shi, Zi-Fa; Kirillov, Alexander M.^*

来源：Dalton Transactions, 2017, 46(33): 10908-10925.

DOI：10.1039/c7dt01742a

• METAL-ORGANIC FRAMEWORKS
• N-DONOR LIGANDS
• SINGLE-CRYSTAL TRANSFORMATION
• PHOTOLUMINESCENCE PROPERTIES
• GAS SORPTION
• COMPLEXES
• SOLVENT
• WATER
• IONS
• HYDROCARBOXYLATION

In this work, a trifunctional N,O-building block, 5-(4-carboxyphenoxy) nicotinic acid (H(2)cpna), that combines three distinct types of functional groups (COOH, N-pyridyl, and O-ether) was used for the hydrothermal assembly of thirteen new coordination compounds: [Co(mu(3)-Hcpna)(2)](n) (1), [Mn(mu(4)-cpna)(H2O)](n) (2), [Mn(mu(4)-cpna)(H2O)(2)](n) (3), [Mn(mu-cpna)(2,2'-bipy)(H2O)(2)](n) (4), {[Ni(mu(3)-cpna)(2,2'-bipy)(H2O)](2)center dot H2O}(n) (5), {[Cd(mu(3)-cpna)(2,2'-bipy)]center dot 2H(2)O}(n) (6), [Zn-2(mu-cpna)(2)(2,2'-bipy)(2)] (7), [Cu(mu-cpna)(2,2'-bipy)(H2O)](n) (8), {[Mn(mu-cpna)(phen) 2]center dot 6H(2)O}(n) (9), {[Ni(mu(3)-cpna)(phen)(H2O)]center dot H2O}(n) (10), [Zn-2(mu-cpna)(2)(phen)(2)] (11), {[Pb(mu 3-cpna)(phen)]center dot H2O}(n) (12), and [Ni(mu(3)-cpna)(4,4'-bipy) 0.5(H2O)] n (13). These products were synthesized from the corresponding metal(II) chlorides, H(2)cpna, NaOH, and optional N-donor supporting ligands or templates {bis(4-pyridyl) amine (bpa), 2,2'-bipyridine (2,2'-bipy), 4,4'-bipyridine (4,4'-bipy), or 1,10-phenanthroline (phen)}. Products 1-13 were characterized in the solid state by standard methods, including elemental and thermogravimetric analysis (TGA), IR spectroscopy, and powder (PXRD) and single-crystal X-ray diffraction. The structures of 1-13 feature distinct structural types, namely the 3D metal-organic frameworks (MOFs 1-3), the 2D coordination polymers (5, 6, 10, 12, and 13), the 1D coordination polymers (4, 8, and 9), and the 0D discrete cyclic dimers (7 and 11). Such a wide structural diversity of 1-13 is driven by various factors, including the type of the metal(II) node, the deprotonation degree of H2cpna, and/or the type of supporting ligand or template. Notably, an addition of bpa can tune the structure of MOF 3 by the template effect. Topological classification of underlying metal-organic networks was performed, leading to several distinct topological nets: rtl (in 1), hxg-d-4-C2/m (in 2), sra (in 3), 2C1 (in 4, 8 and 9), fes (in 5, 10, and 12), hcb (in 6), and 3,4L83 (in 13). The magnetic behavior of 1-5, 8-10, and 13 was studied and theoretically modeled, disclosing antiferromagnetic interactions. The luminescence behavior of 6, 7, 11, and 12 was also investigated.

• 出版日期2017-9-7
• 单位兰州大学