Ten multifunctional cobalt(II) coordination polymers with the formulas of [Co(L 1 )0.5(5-AIP)]·H2O (1), [Co(L 2 )(5-AIP)(H2O)2] (2), [Co(L 3 )0.5(5-AIP)] (3), [Co(L 4 )0.5(5-AIP)(H2O)]·2H2O (4), [Co(L 5 )(5-AIP)] (5), [Co(HBTC)(L 3 )]·H2O (6), [Co(HBTC)(L 6 )(H2O)]·3H2O (7), [Co(L 2 )(1,3-BDC)(H2O)2] (8), [Co2(L 3 )2(1,3-BDC)2]·4H2O (9), and [Co2(L 4 )1.5(1,2-BDC)(μ2-OH)(μ3-OH)(H2O)]·H2O (10) have been prepared by a hydrothermal technique employing six flexible bis(pyridylamide) ligands with different spacers (L 1 = N,N′-bis(3-pyridyl)oxamide, L 2 = N,N′-bis(3-pyridyl)malonamide, L 3 = N,N′-di(3-pyridyl)succinamide, L 4 = N,N′-bis(3-pyridyl)adipamide, L 5 = N,N′-bis(3-pyridyl)heptandiamide, L 6 = N ,N′-bis(3-pyridyl)sebacicdiamide) and four aromatic polycarboxylic acids mixed ligands (5-H2AIP = 5-aminoisophthalic acid, H3BTC = 1,3,5-benzenetricarboxylic acid, 1,3-H2BDC = 1,3-benzenedicarboxylic acid, and 1,2-H2BDC = 1,2-benzenedicarboxylic acid). Compound 1 exhibits a two-dimensional (2D) double-layer network. Compounds 2 and 8 are isostructural and possess one-dimensional (1D) circle-connecting-circle chain structures derived from 1D [Co(L 2 )] n “Ω”-like chain and 1D [Co(5-AIP)] n /[Co(1,3-BDC)] n wavelike chain. Compound 3 possesses a 3,8-connected three-dimensional (3D) coordination framework with {42.6}2{44.610.79.85} topology. Compound 4 is a 2D network containing a ladder-like chain. Compound 5 reveals a novel 3-fold interpenetrating CdSO4-like framework. Compound 6 is a double-layer coordination network with a (3,5)-connected {42·67·8}{42·6} topology. Complex 7 shows a 2D (4,4) grid layer. Compound 9 features a 2-fold interpenetrating 3D α-Po-related topological framework. Compound 10 is a 6-connected 3D coordination polymer with a {412.63} topology. The spacer length of the bis(pyridylamide) ligands, as well as the substituent group and carboxyl group number of polycarboxylates, shows a significant effect on the ultimate architectures of various cobalt(II) compounds 1–10. The electrochemical behaviors of carbon paste electrodes (CPEs) bulk-modified by compounds 1–10 and the electrocatalytic activities of 1-, 6-, 9-, 10-CPEs have been investigated. The photocatalytic properties of compounds 1–10 toward the degradation of methylene blue (MB) in visible light irradiation have been investigated. The variable temperature magnetic susceptibilities for compounds 3, 5, 9, and 10 indicate the existence of antiferromagnetic exchange interactions.
Thirteen new Cu II coordination polymers, namely, (1,3,5-HBTC)] ( 1), hexane, 1,3,5-H 3 BTC = 1,3,5-benzenetricarboxylic acid, 1,2-H 2 BDC = 1,2-benzenedicarboxylic acid, 1,3-H 2 BDC = 1,3-benzenedicarboxylic acid and 1,4-H 2 NDC = 1,4-naphthalenedicarboxylic acid]. Complexes 1−3 based on the same auxiliary ligand show various structures. Complex 1 features a one-dimensional (1D) ∞-like double-chain structure, which consists of a [Cu-1,3,5-HBTC] n chain and [Cu-3-dppa] n meso-helical chain. Complex 2 possesses a (2,4) undulated honeycomb (hcb) net. Complex 3 is a 3-fold interpenetrating three-dimensional (3D) framework, which shows trinodal (2,3,3)-connected topology with the Schlafi symbol of (10•12 2 ) 2 (10 3 ) 2 (12). Complexes 4−6 with 1,2-BDC as secondary ligand exhibit different two-dimensional (2D) layer structures. Complex 4 exhibits a 2D (2,4)-connected (4•12 4 •14)(4) net. Complexes 5 and 6 have similar structures and show 2D networks with undulated sql topology. For complexes 7−10 based on 1,3-BDC secondary ligand, complex 7 shows a 1D zigzag chain, while complexes 8−10 have similar wave-like 2D structures. When 1,4-NDC was used as the auxiliary ligand, complex 11 is a 2D puckered (4,4) network, complex 12 reveals a 4-connected topology with the point symbol of (4 4 •6 2 ), while complex 13 exhibits a 3-fold interpenetrating 3D α-Po framework. The structural diversity indicates that the bis-pyridyl-bis-amide ligands with different spacers and the aromatic polycarboxylates play important roles in tuning the dimensionalities and structures of the title complexes. The fluorescent and photocatalytic properties for 1−13 have also been investigated in detail.
5Metal-organic coordination polymers (MOCPs) are well known organic-inorganic hybrids with infinite structures consisting of metal ions/clusters and organic ligands linked through coordination interactions. MOCPs can be constructed from one or more than one organic bridging ligands (mixed-ligands) and different metal ions. The previous reports prove the fact that the nature of organic ligands and metal ions dominates the final structures as well as properties of the MOCPs in a certain way. Therefore, we focus 10 on discussing the cobalt(II)/copper(II) coordination polymers constructed from the mixed-ligands of polycarboxylates and N-donor ligands, which may possess potential applications in the fields of electrochemistry, electrocatalysis, magnetism and photocatalysis. In this review, we summarize some typical Co(II)/Cu(II) MOCPs based on the mixed bridging organic ligands, aimed to discuss their versatile synthesis methods, topologies and structural influence factors, as well as their tunable properties. 15 All of these aspects are highlighted in this review, which seeks to guide further investigations of cobalt(II)/copper(II) coordination polymers. 65 shown that bis(imidazole)/bis(triazole)/bis(pyridyl) derivatives and polycarboxylate ligands represent the most reliable and typical building blocks which can be jointly applied to synthesize a wide range of desired coordination networks. 13-16 A choice of such connectors in coordination assembly can be rationalized 70 based on the following considerations: (i) the neutral N-donor ligands normally bind to the cobalt(II)/copper(II) ions as the rodlike bidentate tectons; (ii) the polycarboxylate ligands can not
Deliberately controlling organic ligand transformation in situ has remained a challenge for the construction of polyoxometalate (POM)-based inorganic-organic hybrids. In this work, four POM-based hybrids assembled from an in situ bifurcating organic ligand-[Cu2(DIBA)4](H3PMo12O40)·6H2O (1), [Cu2(DIBA)4](H4SiW12O40)·6H2O (2), [Ag(HDIBA)2](H2PMo12O40)·2H2O (3), [Ag3(HDIBA)2(H2O)][(P2W18O62)1/2]·4H2O (4) (DIBAH = 3,5-di(1H-imidazol-1-yl) benzoic acid)-have been designed and obtained under hydrothermal conditions. Compounds 1 and 2 are isostructural, displaying a three-dimensional (3D) 2-fold interpenetrating framework with two types of channels, and the bigger channels are occupied by Keggin polyoxoanions and crystallization water molecules, but only crystallization water molecules in the smaller ones. Compound 3 displays a 3D supramolecular structure constructed from {Ag(HDIBA)2} segments and PMo12O40(3-) polyoxoanions through hydrogen bonding interactions. Compound 4 shows a 3D 2-fold interpenetrating framework based on (3, 3, 4)-connected network, which is constructed from {Ag3(HDIBA)2}n chains and P2W18O62(6-) polyoxoanions as linkers. The DIBAH ligand was generated in situ from 3,5-di(1H-imidazol-1-yl)benzonitrile by deliberate design, which illustrates that the strategy to construct novel POM-based hybrids by controlling ligand transformation in situ is rational and feasible. In addition, the effects of the central metal and POMs on the structures of the target compounds were discussed. Finally, the electrochemical and photocatalytic properties of compounds 1-4 have been investigated in this paper.
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