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Two isomeric zeolite-like metal–organic frameworks with the formula of [(CH3)2NH2][Cd(TPO)]·xsolvent were successfully prepared and characterized. Both frameworks are constructed from tetrahedral TPO3− nodes and tetrahedrally connected Cd2+ nodes, representing rare examples of zeolite-like MOFs with an isomeric characteristic. Moreover, one of the frameworks shows mechanically responsive luminescence emission after the crystals are ground for different times. Additionally, it has permanent porosity, and can selectively adsorb CO2 over N2. [ABSTRACT FROM AUTHOR]

Two unique heterometallic cluster organic frameworks, [Cd4MnIII4MnII6(Tri)4(CH3COO)14(μ4‐O)2(μ3‐O)2(H2O)2] Cd(H2O)2⋅9 H2O (1) and Cu[Cd5Cu6(Tri)4(CH3COO)9(H2O)4]2(CH3COO)3⋅24 H2O (2) (H3Tri=2‐(hydroxymethyl)‐2‐(pyridine‐4‐yl)‐1,3‐propanediol), have been successfully prepared by employing a bifunctional tripodal alcohol ligand as a structure‐directing agent. Crystal structure analyses reveal that 1 represents a rare example of frameworks constructed from Cd−Mn heterometallic chains, and 2 is the first heterometallic MOF based on highest‐nuclear Cd−Cu heterometallic cluster building blocks. Furthermore, the magnetic properties and gas adsorption abilities of 1 and 2 were systematically studied. [ABSTRACT FROM AUTHOR]

In this paper, we report a series of novel mixed‐metal‐substituted organic‐inorganic hybrid polyoxometalates (POMs) H3[(CH3)4N]14[NaLn(PW11O39)3]·18H2O (1‐Ln, Ln = Nd, Sm, Eu) via one‐pot solvothermal synthesis methods, which present the first series of polyoxometalate trimers composed of both alkali‐metal‐ and lanthanide‐substituted keggin‐type POMs. The trimeric heterometallic polyoxoanions in 1‐Ln show an interesting linear arrangement and can be further packed together to generate a packing structure with cations [(CH3)4N]+ and H3O+ filling the gaps between polyoxoanions. Compounds 1‐Ln are characterized by single‐crystal X‐ray diffraction analysis, TGA, IR and PXRD. Additionally, the luminescence and proton conductive properties of 1‐Ln are also characterized. A series of unprecedented linear mixed‐metal‐substituted organic‐inorganic hybrid polyoxometalate trimers H3[(CH3)4N]14[NaLn(PW11O39)3]·18H2O (1‐Ln, Ln = Nd, Sm, Eu), composed of both alkali‐metal‐ and lanthanide‐substituted keggin‐type POMs, show interesting luminescence and proton conductive properties. [ABSTRACT FROM AUTHOR]

During the past decade, research on the design and synthesis of zeolite‐like metal–organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite‐like cluster organic frameworks (ZCOFs) built from 4‐connected metal‐cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra‐large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite‐like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal–halide cluster SBUs, 2) ZCOFs based on metal–oxygen cluster SBUs, 3) ZCOFs based on metal–chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal‐cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed. A frame of reference: Zeolite‐like cluster organic frameworks (ZCOFs) built from 4‐connected metal‐cluster secondary building units (SBUs) have attracted sustained interest due to their charming structures and potential applications in materials sciences. This Minireview presents a summary of recent advances in the development of ZCOF materials. Challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed. [ABSTRACT FROM AUTHOR]

Two rare mixed-cluster-organic frameworks (CH3NH3)3[Cu4-(μ3-O)2(Lb)4][MnMo6O18(La)2]·4NMF·5H2O (1) and [(CH3)2NH2]3[Co5-(μ3-O)2(Lb)6]-[MnMo6O18(La)2]·5DMF (2) (La = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol; Lb = 4-(2-(4-pyridyl)ethenyl) benzoic acid; NMF = N-methylformamide; DMF = N,N-dimethylformamide) have been obtained, exhibiting the first two porous materials simultaneously integrating polyoxometalates and transition-metal–oxygen clusters as secondary building units (SBUs). [ABSTRACT FROM AUTHOR]

Four indium-based heterometallic metal-organic frameworks In3M(IMDC)3(NO3)2(H2O)6 ·solvent ( 2-M, M = Mn, Co, Zn, Mg, H3IMDC = imidazole-4,5-dicarboxylic acid) have been made under solvothermal conditions, and are characterized by single-crystal X-ray diffraction studies, energy-dispersive X-ray spectroscopy, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction analysis. Structural analysis indicates that 2-M exhibit 3D porous frameworks generated by linking three intersecting 1D In-IMDC helical chains with different M2+ ions. Powder X-ray diffraction studies reveal that 2-M exhibit good thermal and water stability. Furthermore, 2-M show moderate gas adsorption abilities that can be modulated by introducing different M2+ ions. Finally, the solid-state luminescent emissions of 2-M at room temperature are also elucidated. [ABSTRACT FROM AUTHOR]

A rare 3-D Mn–organic framework, [(CH3)2NH2]3[Mn5(btc)4(Ac)(H2O)4]·5H2O (1), based on pentanuclear manganese clusters as building blocks has been prepared and structurally characterized by EA, IR, TGA, PXRD, and single-crystal X-ray diffraction. Structural analysis indicates the pentanuclear manganese cluster in1has a bow-like configuration, which is the first found to act as secondary building unit in the field of metal–organic framework. Gas adsorption measurements reveal that1can absorb a considerable amount of N2and CO2. [ABSTRACT FROM AUTHOR]

Two novel types of lithium clusters,Li4tetramer andLi2dimer, have been created as the building blocks ofMOFs. The assembly of such unprecedented clusters with two types oftricarboxylate ligands leads to two highly open frameworks, one ofwhich exhibits a very high CO2uptake capacity among Li-basedMOFs. The work reveals the interesting and unprecedented structuralchemistry of lithium ions. [ABSTRACT FROM AUTHOR]

In this review, the recent advancements of POMOFs and POMOPs, including their assembly methodologies, classification and related applications are summarized. Moreover, the current challenges in the design and fabrication of POMOFs and POMOPs as well as the great potential in these two areas are also discussed. • The recent advancements of POMOFs and POMOPs are summarized. • The advantages of using POM clusters to construct POMOFs and POMOPs are summarized. • Synthetic strategies for further development of POMOFs and POMOPs are presented. • Understanding the structure-property relationships of POMOFs and POMOPs. • The current challenges and the great potential of POMOFs and POMOPs are discussed. During the past two decades, the search of strategies to introduce polyoxometalate (POM) clusters as secondary building units (SBUs) to construct porous extended POM-organic frameworks (POMOFs) and discrete POM-organic polyhedra (POMOPs) have attracted sustained interests because such materials not only integrate the advantages of both POMs and framework/polyhedra structures, but also exhibit good prospects in photo-/electro-catalysis, separation, molecular recognition, host-guest chemistry and so on. In this review, the recent advancements of POMOFs and POMOPs, including their assembly methodologies, classification and related applications are summarized. Moreover, the current challenges in the design and fabrication of POMOFs and POMOPs as well as the great potential in these two areas are also discussed. [ABSTRACT FROM AUTHOR]

Two new luminescent metal-organic frameworks (MOFs), namely {[Cd(μ 2 -CN) 1/2 (1,4-BDC)(H 2 O)] 2 (p-tr 2 Ph)}∙2H 2 O (1) and [Cd 2 (1,4-BDC) 2 (H 2 O) 2 ] 2 (p-tr 2 Ph) (2) (1,4-H 2 BDC ​= ​1,4-dicarboxybenzene, p-tr 2 Ph ​= ​1,4-phenylene-4,4'-bis(1,2,4-triazole)) have been solvothermally synthesized and characterized. Single-crystal structural analysis reveals that compounds 1 and 2 show 3-fold and 4-fold interpenetrated 3-dimensional framework structures, respectively. Interestingly, 1 and 2 show unique luminescent emissions when they were excited under ultraviolet light with wavelength of 330 ​nm. For 1 , the luminescent emission intensity decreased as the temperature rose. While for 2 , the luminescent emission intensity firstly increased as the temperature rose from 80 to 130 ​K but it decreased when the temperature is above 130 ​K. In addition, the temperature-dependent luminescent emissions of both compounds show good linearity and reversibility in a wide range of temperatures, suggesting that 1 and 2 can serve as potential thermometers in specific areas. Two new luminescent metal-organic frameworks with 3-fold and 4-fold interpenetrated structures have been solvothermally synthesized and characterized. Compounds 1 and 2 exhibited distinct luminescent emission. In compound 1, the emission intensity decreased as the temperature rose. While in compound 2, the emission intensity firstly increased as the temperature rose from 80 to 130 ​K but it decreased when the temperature was above 130 ​K. [Display omitted] • Two metal-organic frameworks have been made and characterized. • The frameworks have nanoscale hexagonal and tetragonal channels. • Compound 1 shows an interesting temperature-dependent luminescent emission. • Compound 2 shows an uncommon luminescent emission behaviour. • This work enriches the structural diversities of temperature-dependent luminescent MOF materials. • This work provides an experimental reference for the design and fabrication of luminescent MOFs for temperature detection. [ABSTRACT FROM AUTHOR]