In this work, by using two kinds of viologen ligands three POM‐based Compounds were obtained under hydrothermal conditions, namely AgI(bmypd)0.5(β‐Mo8O26)0.5 (1) (bmypd ⋅ ...2Cl=1,1′‐Biphenyl‐4,4′‐bis(methylene)bis(4,4′‐bipyridyinium)dichloride), AgI2(bypy)4(HSiW12O40)2 ⋅ 14H2O (2) and AgI(bypy)(γ‐Mo8O26)0.5 (3) (bypy⋅Cl=1‐Benzyl‐4,4′‐bipyridyinium chloride). The structures were characterized by Fourier transform infrared spectroscopy (FT–IR), Powder X‐ray diffraction (PXRD), X‐ray photoelectron spectroscopy (XPS) and single crystal X‐ray diffraction. Compounds 1–3 show excellent photochromic ability with fast photoresponse under the irradiation of ultraviolet light with different degrees of color changes. So compounds 1–3 can be used as visible ultraviolet detectors. Compounds 1–3 also possess photoluminescence properties with fast and excellent fluorescence quenching effect. Compounds 1–3 also can be used as inkless and erasable printing materials with suspensions of 1–3 applied to filter paper. Compounds 1–3 can also produce color changes in amine vapor environment, especially in an NH3 atmosphere. Compounds 1–3 can be used as organic amine detectors.
Three polyoxometalate‐viologen Compounds were designed and constructed by using two viologen ligands. Compounds 1–3 show excellent photochromic features with fast photoresponse under irradiation of ultraviolet light with different degrees of color changes. These Compounds exhibit amine detecting and inkless and erasable printing properties, and they can be prepared into a mixed matrix film as a good UV detector.
Three series of copper–lanthanide/lanthanide coordination polymers (CPs) LnIIICuIICuI(bct)3(H2O)2 Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Er (10), Yb (11), and Lu ...(12), H2bct=2,5‐bis(carboxymethylmercapto)‐1,3,4‐thiadiazole acid, LnIIICuI(bct)2 Ln=Ce (2 a), Pr (3 a), Nd (4 a), Sm (5 a), Eu (6 a), Gd (7 a), Tb (8 a), Dy (9 a), Er (10 a), Yb (11 a), and Lu (12 a), and LnIII2(bct)3(H2O)5 Ln=La (1 b), Ce (2 b), Pr (3 b), Nd (4 b), Sm (5 b), Eu (6 b), Gd (7 b), Tb (8 b), and Dy (9 b) have been successfully constructed under hydrothermal conditions by modulating the reaction time. Structural characterization has revealed that CPs 1–12 possess a unique one‐dimensional (1D) strip‐shaped structure containing two types of double‐helical chains and a double‐helical channel. CPs 2 a–12 a show a three‐dimensional (3D) framework formed by CuI linking two types of homochiral layers with double‐helical channels. CPs 1 b–9 b exhibit a 3D framework with single‐helical channels. CPs 6 b and 8 b display visible red and green luminescence of the EuIII and TbIII ions, respectively, sensitized by the bct ligand, and microsecond‐level lifetimes. CP 8 b shows a rare magnetic transition between short‐range ferromagnetic ordering at 110 K and long‐range ferromagnetic ordering below 10 K. CPs 9 a and 9 b display field‐induced single‐chain magnet (SCM) and/or single‐molecule magnet (SMM) behaviors, with Ueff values of 51.7 and 36.5 K, respectively.
Time‐dependent assembly: Three series of copper–lanthanide/lanthanide coordination polymers have been successfully prepared under hydrothermal conditions by modulating the reaction time and structurally characterized (see figure). Their syntheses, structures, photoluminescence, and magnetism have been systematically investigated.
Metal-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 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, aiming to discuss their versatile synthesis methods, topologies and structural influence factors, as well as their tunable properties. All of these aspects are highlighted in this review, which seeks to guide further investigations of cobalt(
ii
)/copper(
ii
) coordination polymers.
Metal-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.
Through using two kinds of bis(pyrazolyl) ligands, four polyoxometalate (POM)-based compounds were hydrothermally synthesized and structurally characterized, Ag3(Hbhpe)2(H2O)(H2PMo12O40)·H2O (1), ...Ag(H2bdpm)2(H2PW12O40)·4H2O (2), Ag6(H2bdpm)6(HPW(VI)8W(V)4O40)·2H2O (2) and Ag4(H2bdpm)4(H2P2W18O62)·3H2O (4) (H2bhpe = 1,2-bis(1-H-pyrazolate)ethane, H2bdpm = 1,1'-bis(3,5-dimethyl-1H-pyrazolate)methane). In compound 1, the Ag-Hbhpe subunit is a 2D layer containing large penta-membered cycles and small tri-nuclear Ag(I) clusters. The Keggin anions covalently float on the large cycles. In compound 2, the Keggin anions are fused by Ag(H2bdpm)2(+) subunits to form a 1D chain. Compound contains hexa-membered metal-organic cycles, which are further linked by Keggin anions to build a 1D chain. Adjacent chains share the Ag(I) ions to construct a 3D framework of 3. Compound 4 exhibits a wavy double-track chain structure, with the Wells-Dawson anions covalently suspended up and down this chain. The steric hindrance of -CH3 groups in H2bdpm leads to the formation of mono-nuclear Ag(I) subunits in 2 - 4. The influence of -CH3 steric hindrance in bis(pyrazolyl) ligands on the structures of 1 - 4 is discussed. The electrochemical and photocatalytic properties of the title compounds have been studied.
Through the use of a flexible ligand 1,1′-bis(3,5-dimethyl-1H-pyrazolate)methane (H
2
bdpm), a K-encapsulated Preyssler-based complex, Cu
4
(H
2
bdpm)
4
(H
2
O)
10
(H
6
KP
5
W
30
O
110
)·2(H
2
...bdpm)·14H
2
O, has been synthesized under hydrothermal conditions. Single crystal X-ray diffraction analysis shows that the complex contains rare K-encapsulated Preyssler anions, which are linked by binuclear cyclic clusters Cu
2
(H
2
bdpm)
2
4+
to form a 1D chain. Adjacent chains are further connected by abundant intermolecular forces to construct a 2D supramolecular framework. The photocatalytic and electrochemical properties of the complex have been investigated.
Graphical abstract
(1) The Preyssler-based POM-TMCs are rarely reported. (2) The K-encapsulated Preyssler anion is uncommonly observed in Preyssler-based compound. (3) Preyssler anions are linked by binuclear Cu
II
clusters to form a 1D chain. (4) Compound
1
exhibits photocatalytic and electrochemical properties.
Three Keggin-based metal–organic complexes have been constructed from two organic ligands 1H-Imdazole-2-carboxylic acid (HL1) and 1H,1′H-Biimdazole-4,4′-dicarboxylic acid (HL2). The HL2 ligand was ...firstly used in the POMs field. The electrochemical behavior of 2, 3 and photocatalytic activities of the title complexes have been studied. Display omitted
•Three Keggin-based complexes have been obtained with two N-heterocyclic carboxylic acids ligands.•Complex 3 shows an uncommonly double Cl-capped tri-nuclear CuI cluster.•The 1H,1′H-Biimdazole-4,4′-dicarboxylic acid ligand is firstly introduced to the POM field.•The electrochemical behavior of 2, 3 and photocatalytic properties and fluorescent properties of 1–3 are studied.
Three metal–organic complexes (MOCs) based on Keggin-type polyoxometalate anions and two organic ligands 1H-Imdazole-2-carboxylic acid (L1) and 1H,1′H-Biimdazole-4,4′-dicarboxylic acid (L2), Ag2(L1)4HPMo12O40·3H2O (1), Ag2(L1)4HPW12O40·H2O (2) and CuI6Cl4(L2)6H3PMo12O40·2NO3 (3), have been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction analyses, elemental analyses and IR spectra. Complexes 1 and 2 are isostructural and contain a supramolecular chain with a –ABAB– style. The adjacent one dimensional (1D) chains through hydrogen bonding interactions form a 2D supramolecular layer. In complex 3, there exist double Cl-capped tri-nuclear Cu+ clusters. Furthermore, the photocatalytic and fluorescent properties of complexes 1–3 and electrochemical behavior of complexes 2 and 3 were investigated.
Two polyoxometalate‐based compounds constructed by Keggin/Ag/L, namely Ag10(L1)6(HL1)2HPMo2VMoVI10O40 (1) and Ag10(L2)8(H2SiMo12O40) (2) (L1 = 1,2,4‐1H‐triazole and L2 = 1H‐tetrazole), were ...synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. In compound 1, the tetra‐nuclear Ag cycles constructed by four L1 ligands, two Ag1 ions, and two Ag2 ions. Compound 1 exhibits a two dimensional (2D) metal‐organic layer containing adjacent tetra‐nuclear Ag cycles. Furthermore, the adjacent 2D layers are further extended by Ag ions to form a three dimensional (3D) channel‐like framework, with Keggin anions embedding in the channels. Compound 2 is isostructural with 1. Additionally, the electrochemical and photocatalytic properties of the title compounds were investigated.
Through using mixed N/S-containing ligand 2-(4-thiazolyl)benzimidazole (
L
), four new metal–organic coordination polymers, namely, Co
2
L
4
(HBTC)(H
2
O)
2
(
1
), Cu
2
L
2
(HBTC)
2
·H
2
O (
2
), Ni
...L
3
·(HBTC)·H
2
O (
3
) and Ni
L
3
·H
2
O (
4
), have been synthesized under hydrothermal conditions, further assisted by a second organic ligand, benzenetricarboxylic (H
3
BTC). The structures of
1
–
4
have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses and IR spectra. Compound
1
contains two {Co
L
2
(H
2
O)} fragments, which are connected by a BTC molecule to form a discrete “V”-type subunit. The hydrogen bonding interactions between N3⋯O1 atoms induce a 1D chain of
1
. Complex
2
includes bi-nuclear Cu
II
subunits, which are linked by BTC ligands to form a 2D layer. Each bi-nuclear Cu subunit is linked by four BTC molecules. Both complexes
3
and
4
are based on Ni
L
3
subunits. In complex
3
, when NiCl
2
·6H
2
O was used as reactant, a discrete BTC molecule is captured as a counter anion. In contrast, when using reactant NiSO
4
·6H
2
O, Ni
L
3
·H
2
O (
4)
is formed. Both complexes
3
and
4
contain abundant hydrogen bonding interactions. In these complexes, the N donors in
L
ligand coordinate with transition metals and the S atoms participate in hydrogen bonding interactions.
Graphical Abstract
Through using mixed N/S-containing ligand 2-(4-thiazolyl)benzimidazole (
L
), four new metal-organic coordination polymers, namely, Co
2
L
4
(HBTC)(H
2
O)
2
(
1
), Cu
L
(HBTC) (
2
), Ni
L
3
·(HBTC)·H
2
O (
3
) and Ni(
L
)
3
·H
2
O (
4
), have been synthesized under hydrothermal conditions further assisted by the second organic ligand benzentricaboxylate (H
3
BTC).
Three new inorganic‐organic hybrid compounds based on α‐Keggin clusters and Ag‐organic subunits, Ag3L4(H2O)4PMo12O40·3H2O (1), Ag3L4(H2O)4PW12O40·2H2O (2), and Ag3L6PMo12O40 (3) L = ...1‐amino‐4‐(3,5‐dimethylpyrazolyl)hydralazine, were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction. Compounds 1 and 2 are isostructural and contain two kinds of Ag subunits: dinuclear Ag2L2(H2O)42+ and mononuclear AgL2+. The dinuclear Ag clusters are linked by Keggin anions to construct a 1D chain, whereas the mononuclear Ag subunits form another supramolecular chain. The adjacent 1D coordination chains and supramolecular chains connect with each other through hydrogen bonding interactions to form a 2D supramolecular layer. In compound 3, the discrete mononuclear subunits AgL2+ are linked by PMo12O403– anions through hydrogen bonding interactions to construct a supramolecular chain. Additionally, the electrochemical and photocatalytic properties of the title compounds were investigated.
