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The anhydrous proton conductivity of Im@IEF-11 resulting from the integration of imidazole and porous IEF-11 has been investigated, and the highest proton conductive value can reach up to 7.64 × 10−2 S cm−1. Furthermore, IEF-11 is also developed to reduce CO2 due to its reasonable structure and suitable energy band, and its CO formation rate is 31.86 μmol g−1 h−1. [ABSTRACT FROM AUTHOR]

The photocatalytic conversion of CO2 into widely adjustable syngas (CO/H2 mixture) has been considered as an extraordinarily promising but challenging strategy to realize high value-added utilization of CO2 to alleviate worldwide environmental problems and energy crisis. To achieve this goal, we report a newly designed crystalline covalent organic framework (COF-TVBT-Bpy) that embedded a series of metal active sites to efficiently convert CO2 and H2O into syngas under visible-light illumination. COF-TVBT-Bpy not only provides a coordination environment for the metal center, but also enhances electron delocalization by the extended conjugated moiety, thus facilitating electron transfer. The optimized Co@COF-TVBT-Bpy achieves the highest photocatalytic CO2-to-syngas conversion efficiency in pure CO2 (up to 2291.1 μmol g−1 h−1, CO/H2 ≈ 1 : 1). The intrinsic reason for a CO/H2 ratio of 1 : 1, electron transfer pathway, and syngas generation mechanism over Co@COF-TVBT-Bpy are explored by the combination of in situ measurements and theoretical calculations. The experimental results confirm that the ratio of CO/H2 can be widely modulated by adjusting the metal active sites and photoreaction conditions. This work proves the immense potential of utilizing COFs as platforms to anchor metal active sites for syngas formation and provides a facile method to regulate the ratio of syngas in a wide range. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) provide an ideal platform for loading various guests owing to their available space, and can be developed as a class of multifunctional materials. Herein, we cover the design and synthesis of two kinds of exchanged frameworks with multifunctional applications based on H3ImDC and In(NO3)3·2H2O through guest exchange inside the framework. The guest ammonium ion (NH4+) and [Ru(2,2′-bipyridine)3]2+ (Rubpy) are selected to exchange the dimethylammonium cation (Me2NH2+) encapsulated within In-MOF, giving birth to two kinds of new MOFs, named NH4+@In-MOF and Rubpy@In-MOF respectively. The proton conduction of NH4+@In-MOF and the CO2 photoreduction of Rubpy@In-MOF are investigated. Under different test conditions, the proton conductive behaviors of NH4+@In-MOF are evaluated and the best proton conductive value can reach up to 9.81 × 10−3 S cm−1. Compared to the original In-MOF, Rubpy@In-MOF exhibits a significantly enhanced CO2 photoreduction performance under a pure CO2 atmosphere. Furthermore, its photocatalytic activity is retained even under a 10% CO2 gas atmosphere, displaying a synergistic effect between Rubpy and In-MOF24 within Rubpy@In-MOF. [ABSTRACT FROM AUTHOR]

Two unprecedented 3D porous anionic metal–organic frameworks, [Me2NH2]2[Cd2(bpdc)3]·4dma 1and [Me2NH2]2[Cd2(NH2bdc)3]·4dma 2(dma = N,N′-dimethylacetamide, bpdc = 4,4′-biphenyldicarboxylate, NH2bdc = 2-amino-1,4-benzenedicarboxylate) have been solvothermally synthesized with a dimethylammonium cations template. Both 1and 2are constructed from low-symmetry SBUs. 1has a chiral framework with helical nanotube-like channels, and 2has a MOF-5-like motif. The fluorescence, N2adsorption and ion-exchange properties for 1have been examined. [ABSTRACT FROM AUTHOR]

Abstract: Three novel polymers, {[Cd(m-bdc)(L)]·H2O} n (1), [Co(m-bdc)(L)0.5(H2O)] n (2) and [Zn5(L)2(p-bdc)5(H2O)] n (3) based on 1,1′-bis(pyridin-3-ylmethyl)-2,2′-biimidazole (L) ligand and benzenedicarboxylate isomers, have been prepared and structurally characterized. Compound 1 exhibits a 2D architecture with (42·6)(42·67·8) topology, which is synthesized by L and 1,3-benzenedicarboxylate (m-bdc) ligands. Compound 2 is constructed from 1D chains that are linked by L ligands extending a 2D (4,4) grid. Compound 3 is a 3D framework with (43)(46·618·84) topology, which is composed of trinuclear clusters and five-coordinated metal centers joined through 1,4-benzenedicarboxylate (p-bdc) and L ligands. Moreover, the fluorescent properties of L ligand, compounds 1 and 3 are also determined. [Copyright &y& Elsevier]

Abstract: A novel three-dimensional (3D) polymer [Cd2(Hbiim)4] n (H2biim=2,2′-biimidazole) 1 was obtained through hydrothermal reaction and characterized by single crystal X-ray diffraction, and the fluorescent property was also determined. Compound 1 crystallizes in a monoclinic chiral space group P21 and contains two types of helical chains. Hbiim− partially deprotonated of H2biim exhibits two different coordination modes, which contributes greatly to the formation of the 3D chiral framework. Compound 1 exhibits blue fluorescence at 488nm in the solid-state upon excitation at 430nm. [Copyright &y& Elsevier]

The title compound, [Cu2Cl4(C20H20N6)], is a dinuclear copper complex. The 1,4-bis­[2-(2-pyrid­yl)imidazol-1-yl]butane ligand bridges two CuII ions, each in a slightly distorted tetra­hedral geometry, consisting of two N atoms from the ligand and two Cl− anions. The molecule is centrosymmetric. [ABSTRACT FROM AUTHOR]

Abstract: Two new lead-carboxylate complexes based on nicotinic acid N-oxide ligand, [Pb(NNO)(FA)0.5] (1) (HNNO=nicotinic acid N-oxide, FA=fumaric acid) and [Pb2(NNO)(BTC)] (2) (H3BTC=1,3,5-benzenetricarboxylic acid) were hydrothermally synthesized and characterized by the elemental analyses, IR spectra and single crystal X-ray diffraction. Significant phosphorescent properties of two compounds were observed at room temperature. [Copyright &y& Elsevier]

The conversion of CO 2 into useful chemicals via photocatalysts is a promising strategy for resolving the environmental problems caused by the addition of CO 2 . Herein, a series of composite photocatalysts MOP@TpPa-CH 3 based on MOP-NH 2 and TpPa-CH 3 through covalent bridging have been prepared via a facile room-temperature evaporation method and employed for photocatalytic CO 2 reduction. The photocatalytic performances of MOP@TpPa-CH 3 are greater than those of TpPa-CH 3 and MOP-NH 2 , where the CO generation rate of MOP@TpPa-CH 3 under 10% CO 2 still reaches 119.25 μmol g -1 h -1 , which is 2.18 times higher than that under pure CO 2 (54.74 μmol g -1 h -1 ). To investigate the structural factors affecting the photocatalytic activity, MOP@TBPa-CH 3 without C═O groups is synthesized, and the photoreduction performance is also evaluated. The controlling experimental results demonstrate that the excellent photoreduction CO 2 performance of MOP@TpPa-CH 3 in a 10% CO 2 atmosphere is due to the presence of C═O groups in TpPa-CH 3 . This work offers a new design and construction strategy for novel MOP@COF composites.

Metal-organic frameworks constructed from Zr usually possess excellent chemical and physical stability. Therefore, they have become attractive platforms in various fields. In this work, two families of hybrid materials based on ZrSQU have been designed and synthesized, named Im@ZrSQU and Cu@ZrSQU, respectively. Im@ZrSQU was prepared through the impregnation method and employed for proton conduction. Im@ZrSQU exhibited terrific proton conduction performance in an anhydrous environment, with the highest proton conduction value of 3.6 × 10 -2 S cm -1 at 110 °C. In addition, Cu@ZrSQU was synthesized via the photoinduction method for the photoreduction of CO 2 , which successfully promoted the conversion of CO 2 into CO and achieved the CO generation rate of up to 12.4 μmol g -1 h -1 . The photocatalytic performance of Cu@ZrSQU is derived from the synergistic effect of Cu NPs and ZrSQU. Based on an in-depth study and discussion toward ZrSQU, we provide a versatile platform with applications in the field of proton conduction and photocatalysis, which will guide researchers in their further studies.

The anhydrous proton conductivity of Im@IEF-11 resulting from the integration of imidazole and porous IEF-11 has been investigated, and the highest proton conductive value can reach up to 7.64 × 10 -2 S cm -1 . Furthermore, IEF-11 is also developed to reduce CO 2 due to its reasonable structure and suitable energy band, and its CO formation rate is 31.86 μmol g -1 h -1 .

The photoreduction deposition method is employed to fabricate a family of silver nanoparticle (Ag NP)-modified polyoxometalate-based metal-organic framework ( NENU-5 ) photocatalysts, named Ag/NENU-5 . The title photocatalysts, Ag/NENU-5 , can be used for the photocatalytic reduction of CO 2 and are observed to efficiently reduce CO 2 into CO, in which the highest reduction rate is 22.28 μmol g -1 h -1 , 3 times greater than that of NENU-5 . Photocatalytic reduction performances of CO 2 have been extremely improved after the incorporation of Ag NPs as the cocatalyst. The enhancement of the photocatalytic reduction of CO 2 has been attributed to the synergistic effects of Ag NPs and NENU-5 , inhibiting the charge recombination during the photocatalytic process and increasing the reaction active sites. Furthermore, the influence of Ag NPs on the photocatalytic activity has also been investigated. The experimental results clearly reveal that the size of Ag NPs could exert a main effect on the photocatalytic activity, and the reasonable size of Ag NPs is able to enhance the photocatalytic reduction activity toward CO 2 significantly.

Metal-organic frameworks (MOFs) provide an ideal platform for loading various guests owing to their available space, and can be developed as a class of multifunctional materials. Herein, we cover the design and synthesis of two kinds of exchanged frameworks with multifunctional applications based on H 3 ImDC and In(NO 3 ) 3 ·2H 2 O through guest exchange inside the framework. The guest ammonium ion (NH 4 + ) and [Ru(2,2'-bipyridine) 3 ] 2+ (Rubpy) are selected to exchange the dimethylammonium cation (Me 2 NH 2 + ) encapsulated within In-MOF , giving birth to two kinds of new MOFs, named NH 4 + @In-MOF and Rubpy@In-MOF respectively. The proton conduction of NH 4 + @In-MOF and the CO 2 photoreduction of Rubpy@In-MOF are investigated. Under different test conditions, the proton conductive behaviors of NH 4 + @In-MOF are evaluated and the best proton conductive value can reach up to 9.81 × 10 -3 S cm -1 . Compared to the original In-MOF , Rubpy@In-MOF exhibits a significantly enhanced CO 2 photoreduction performance under a pure CO 2 atmosphere. Furthermore, its photocatalytic activity is retained even under a 10% CO 2 gas atmosphere, displaying a synergistic effect between Rubpy and In-MOF24 within Rubpy@In-MOF .

It is a promising strategy to prepare composite photocatalysts based on MOFs and semiconductors for enhancing photocatalytic reduction of carbon dioxide (CO 2 ). A family of binary composite photocatalysts ( CdS@UiO-66-NH 2 ) with different CdS contents have been designed and synthesized, which have been explored for photocatalytic reduction of CO 2 . CdS@UiO-66-NH 2 can efficiently convert CO 2 into CO under visible light irradiation via the solid-gas mode in the absence of sacrificial agents and photosensitizers. The generation rate of CO can reach up to 280.5 μmol g -1 h -1 , which is 2.13-fold and 2.9-fold improvements over the pristine CdS and UiO-66-NH 2 , respectively, and the selectivity for CO is very high. Furthermore, this kind of photocatalysts can still maintain great photocatalytic activity in CO 2 /N 2 mixed atmosphere with different CO 2 concentrations. The outstanding performances of CdS@UiO-66-NH 2 may be attributed to the existence of the direct Z-scheme heterojunction, which possesses the enhanced separation and migration of photo-generated charge carriers between UiO-66-NH 2 and CdS, available specific surface areas and improved visible light absorption ability as well as abundant reaction active sites. This case reveals that MOF-based composite photocatalysts exhibit promising potential applications in the field of CO 2 conversion.

Two unprecedented 3D porous anionic metal-organic frameworks, [Me2NH2]2[Cd2(bpdc)3].4dma 1 and [Me2NH2]2[Cd2(NH2bdc)3].4dma 2 (dma = N,N'-dimethylacetamide, bpdc = 4,4'-biphenyldicarboxylate, NH(2)bdc = 2-amino-1,4-benzenedicarboxylate) have been solvothermally synthesized with a dimethylammonium cations template. Both 1 and 2 are constructed from low-symmetry SBUs. 1 has a chiral framework with helical nanotube-like channels, and 2 has a MOF-5-like motif. The fluorescence, N2 adsorption and ion-exchange properties for 1 have been examined.

A series of mixed-ligand coordination complexes, namely [Zn(L(1))(oba)] (), [Cd(L(1))(oba)] (), [Zn(2)(L(2))(oba)(2)].8H(2)O (), [Cd(2)(L(2))(oba)(2)].2H(2)O (), [Zn(3)(L(3))(oba)(3)] (), [Cd(2)(L(3))(oba)(2)].(L(3)) (), [Cd(L(4))(oba)].H(2)O () and [Cd(L(5))(oba)].3H(2)O (), where L(1) = 2-(2-pyridyl)imidazole, L(2) = 1,4-bis[2-(2-pyridyl)imidazol-1-yl]butane, L(3) = 1,4-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene, L(4) = 1,3-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene, L(5) = 1,2-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene and H(2)oba = 4,4'-oxydibenzoic acid, have been synthesized under hydrothermal conditions. Their structures have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. In compounds and , oba(2-), L(1) ligand and Zn(II) or Cd(II) ions assemble to form the parallel chains or parallel sheets which are linked by the weak hydrogen bonding and pipi stacking interactions to give the 2D supramolecular sheet or 3D supramolecular net, respectively. For , L(2) ligands connect [Zn(oba)] chains to generate a unusual (10,3)-b topological structure which is the first example for eight-fold interpenetrating framework based on the (10,3)-b net. In , L(2) ligands link [Cd(oba)] double-chains to give a 2D sheet which is assembled by pipi stacking interactions to obtain a 3D supramolecular net. In , L(3) ligands link Zn(II) ions from alpha-Po net formed by Zn(II) ions and oba(2-) anions to show a novel 3D 8-connected self-penetrating framework with the unreported (4(16).6(11).8) topological structure. In , the double-chains constructed by Cd(II) and oba(2-) anions are linked by one kind of L(3) ligand to form a layer-like structure which is assembled by pipi stacking interactions to show a 3D supramolecular structure. In , oba(2-) anions coordinate to Cd(II) cations to form chains which are connected by L(4) to form a four-fold interpenetrating diamond network. In , the weak hydrogen bonding and pipi stacking interactions connect the [Cd(L(5))(oba)] chains to give a 2D supramolecular sheet. By careful inspections of the structures of , we believe that the different flexible and angular neutral ligands, coordination geometries of metal centers and weak interactions (hydrogen bonds and pipi stacking interactions) are crucial factors for the formation of the different structures. The photoluminescent properties of have been studied in the solid state at room temperature.

Inorganic-organic hybrid materials based on Keggin polyoxometalate building blocks combined with Cu(II)/Cu(I) and flexible fluconazole ligand [1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-1-yl)methyl]methanol] (Hfcz) have been obtained by hydrothermal methods, namely, [Cu(II)(2)(Hfcz)(4)(SiW(12)O(40))].3H(2)O (1), [Cu(II)(4)(fcz)(4)(H(2)O)(4)(SiMo(12)O(40))].6H(2)O (2), [Cu(II)(2)(fcz)(2)][Cu(II)(4)(fcz)(4)(SiW(12)O(40))][Cu(II)(2)(fcz)(2)(H(2)O)(2)(SiW(12)O(40))].6H(2)O (3), (Et(3)NH)(2)[Cu(I)(2)(Hfcz)(2)(SiW(12)O(40))].2H(2)O (4), (Et(3)NH)(2)[Cu(I)(2)(Hfcz)(2)(SiW(12)O(40))].H(2)O (5) and [Cu(I)(4)(Hfcz)(4)(SiMo(12)O(40))] (6). Their structures have been determined by single-crystal X-ray diffraction analyses, and the compounds are further characterized by elemental analyses, IR spectra and thermogravimetric (TG) analyses. In 1, Cu(II) cations are bridged by fluconazole ligands to form a 3D lvt coordination polymeric network, which is connected by (SiW(12)O(40))(4-) anions to form a complicated 3D (4,6)-connected framework with the topology of (4(2).6(4))(4(6).6(7).8(2))(2). In 2, two fcz(-) anions chelate two Cu(2+) cations to form a [Cu(fcz)](2)(2+) dimer, which is bridged by (SiW(12)O(40))(4-) polyanions to generate a 2D (4,4) grid. Compound 3 is formed by three types of co-crystallizing subunits including a dimer [Cu(fcz)](2)(2+), a dumbbell molecule [Cu(4)(fcz)(4)(SiW(12)O(40))] and an infinite chain {[Cu(2)(fcz)(2)(H(2)O)(2)(SiW(12)O(40))](2-)}(infinity). In compounds 4 and 5, Hfcz ligands link Cu(+) cations to generate 1D coordination polymeric units, and (SiW(12)O(40))(4-) polyanions connect these metal-organic units to form two types of (6(3)) sheets which are topological isomerism. In compound 6, (SiMo(12)O(40))(4-) polyanions fixed in Cu(I)-Hfcz square rings are further extended into a 2D sheet via linking Cu(I) atoms of different rings. By carefully inspection of the structures of 1-6, it is believed that various transition-metal organic units and Keggin polyanions with different coordination modes are important for the formation of the different structures. In addition, electrochemical behaviors of compounds 1, 2, 5 and 6 have been investigated.

In the title compound, [Ni(C(10)H(6)NO(3))(2)(H(2)O)(4)], the central Ni(II) atom is located on an inversion center and coordinated in a slightly distorted octa-hedral geometry by two O atoms from two 2-oxo-1,2-dihydro-quinoline-4-carboxyl-ate ligands and four water mol-ecules, all of which act as monodentate ligands. The crystal structure features an extensive network of inter-molecular hydrogen-bonding inter-actions (O-H⋯O and N-H⋯O) and offset face-to-face π-π stacking inter-actions [centroid-centroid distances = 3.525 (3) and 3.281 (5) Å].