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This work demonstrates a feasible strategy for the synthesis of new zeolite-like framework materials. With the strategy of using two different supertetrahedral clusters as secondary building units, two new heterometallic zeolite-like frameworks with isomeric structures but tunable topologies were first made. Besides, the porous nature and the proton conduction performance of the new materials were further studied. [ABSTRACT FROM AUTHOR]

A series of 3d–4f heterometallic cluster incorporated polyoxoniobates (PONbs) with different magnetic properties were first made and characterized. This work not only provides a promising strategy to make new heterometallic cluster incorporated PONbs but also demonstrates an ideal model to probe how transition-metal ions influence the magnetic property of PONbs. [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]

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]

A series of polyoxometalates (POMs) that incorporate the highest-nuclearity Ln clusters that have been observed in such structures to date (Ln26 , Ln=La and Ce) are described, which exhibit giant multishell configurations (Ln⊂W6⊂Ln26⊂W100). Their structures are remarkably different from known giant POMs that feature multiple Ln ions. In particular, the incorporated Ln-O clusters with a nuclearity of 26 are significantly larger than known high-nuclearity (≤10) Ln-O clusters in POM chemistry. Furthermore, they also contain the largest number of La and Ce centers for any POM reported to date and represent a new kind of rare giant POMs with more than 100 W atoms. Interestingly, the La26-containing POM can undergo a single-crystal to single-crystal structural transformation in the presence of various transition-metal ions, such as Cu2+, Co2+, and Ni2+, from an inorganic molecular nanocluster into an inorganic-organic hybrid extended framework that is built from POM building blocks with even higher-nuclearity La28 clusters bridged by transition-metal complexes. [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]

Abstract: A series of new polyoxometalates based on [Ni6(μ3-OH)3(H2O)6(en)3(B-α-PW9O34)] (en=ethylenediamine) clusters capped by different tripodal alcohol ligands have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray diffraction, respectively. The experimental results indicate that the tripodal alcohol ligands can substitute three hydroxyl groups located on the axial positions of the Ni6 cluster to form new polyoxometalates with different substituted modes. [Copyright &y& Elsevier]

Reported here is a lithium cubane based zeolitic framework possessing a multi-dimensional channel system. The unique design strategy of adopting the ditopic ligand 4-pyridinol leads to a rigid porous framework with high thermal stability. It has a BET surface area of 440.3 m2g−1and a H2uptake capacity of 108.7 cm3g−1at 77 K. [ABSTRACT FROM AUTHOR]

A series of novel 4s–4f heterometallic cluster substituted polyoxometalates (POMs) with formula of H 9 Na 12 K 2 [K 3 Ln 4 (NO 3) 2 (GeW 10 O 37) 2 (Ge 2 W 18 O 66)]·34H 2 O (1-Ln) (Ln = Dy, Ho, Er) have been hydrothermally made by adopting a trilacunary [A-α-GeW 9 O 34 ]10− as a precursor. 1-Ln represent the first examples of metal-substituted POM clusters based on mixed POM fragments including dilacunary [α-GeW 10 O 37 ]10− and multilacunary open Well-Dawson [Ge 2 W 18 O 66 ]16− fragments. • Novel 4s–4f heterometallic substituted POMs have been prepared and characterized. • The compounds contain mixed Keggin/ open Well-Dawson POM fragments. • The Luminescent properties of these compounds were systematically studied. • The work enriches the diversity of heterometallic metal cluster substituted POMs. • This work provides a new route for making new POMs based on mixed POM units. By adopting a trilacunary [A-α-GeW 9 O 34 ]10− as a precursor under hydrothermal conditions, a series of novel 4s–4f cluster substituted polyoxometalates (POMs) containing two types of in situ generated lacunary POM fragments have been made. These compounds were characterized by single-crystal X-ray diffractions, powder X-ray diffractions, infrared spectroscopy, thermogravimetric analyses, respectively. Structural analyses indicate that these compounds constructed from a seven-nuclearity K-O-Ln (Ln = Dy, Ho, Er) heterometallic cluster stabilized by mixed dilacunary Keggin [α-GeW 10 O 37 ]10−/multilacunary open Wells-Dawson [Ge 2 W 18 O 66 ]16− fragments. Furthermore, the solid luminescent properties of the compounds at room temperature were studied. [ABSTRACT FROM AUTHOR]