cg300442b_si_002.cif (252.24 kB)
pH and Auxiliary Ligand Influence on the Structural Variations of 5(2′-Carboxylphenyl) Nicotate Coordination Polymers
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posted on 2016-02-20, 20:09 authored by Jinzhong Gu, Zhuqing Gao, Yu TangA ligand 5-(2′-carboxylphenyl) nicotic acid (H2cpna) has been successfully applied to construct a series
of coordination
complexes {[Cd(Hcpna)2(H2O)2]·3H2O}n (1), [Cd(cpna)(H2O)]n (2), [M(cpna)(2,2′-bipy)(H2O)]n (M = Cd (3),
Co (4), and Mn (5)), [Co(cpna)(phen)(H2O)]n (6), [Mn(cpna)(phen)(H2O)]n (7), {[Nd(Hcpna)(cpna)(H2O)2]·3H2O}n (8), and {[Ln(Hcpna)(cpna)(phen)]·2H2O}n (Ln = Pr (9),
Nd (10), Eu (11), and Gd (12), 2,2′-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline)
under hydrothermal conditions. By adjusting the reaction pH, H2cpna ligand is partially deprotonated to form Hcpna– in 1 and completely deprotonated to create cpna2– in 2–7, and both
forms are observed in 8–12. Complexes 1–5 and 8 possess two-dimensional
(2D) layered structures, which are further extended into 3D metal–organic
supramolecular frameworks by C–H···O hydrogen
bond and/or π–π stacking interactions. Complexes 6, 7, and 9–12 exhibit one-dimensional (1D) chain structures, which further build
three-dimensional (3D) supramolecular architecture via C–H···O
hydrogen-bonding and/or π–π stacking interactions.
The results revealed that the pH value of the reaction system and
auxiliary ligand play an important role in determining the structures
of the complexes. Magnetic susceptibility measurements indicate that
compounds 4–10 and 12 have dominating antiferromagnetic couplings between metal centers.
Furthermore, thermal stabilities for 1–12 and luminescent properties for 1–3, and 11 are also discussed in detail.
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Keywords
Structural Variationssupramolecular architectureH 2cpnahydrothermal conditionspH valuereaction systemMnComplexenicotic acidinteractionchain structuresNdCoAuxiliary Ligand InfluenceLndeprotonatedmetal centerscomplexreaction pHH 2cpna ligandantiferromagnetic couplingsMagnetic susceptibility measurements
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