Cluster Organic Frameworks Research Articles

Photoactive Cluster-Organic frameworks with 1D Cu-I chain

Presented here is a photoactive cluster-organic frameworks with 1D Cu-I chain, namely (Cu2I)(pytz) (1) (Hpytz = 5-(4′-pyridyl)tetrazole). Compound 1 features a unique 1D Cu-I chain constructed from a Cu3I2 cluster. These chains are interconnected by the tetrazole moiety of pytz, forming a 2D layer. Furthermore, the pyridine moiety of pytz acts as pillars, creating a pillar-layered framework. Moreover, compound 1 displays strong photoluminescence, excellent visible light adsorption, and remarkable photocatalytic activity for the degradation of methylene blue under visible light conditions. These properties highlight the potential applications of these frameworks in areas such as optoelectronics and environmental remediation.

Ligand regulation and capacitive properties of nickel based pyrazole trinuclear copper cluster organic framework

Traditional metal organic framework (MOF) hinders its application as high-performance electrode materials for supercapacitors due to the limited electron transfer efficiency and conjugation of its ligand molecules. Therefore, in this article, highly electrochemical active pyrazole trincore-copper cluster derivatives as the core unit were covalently assembled by Schiff base reaction with organic linkers of different structures to obtain a series of structurally different electroactive ligands. It was found that ligands with multiactive metal chelation site structure with polydentate carboxylate linker and aromatic extension showed high coordination ability and high degree of conjugation. The nickel-based MOF synthesized with this novel electroactive ligand exhibited a high specific capacitance of 1804 Fg−1 at a current density of 1 Ag−1. At a power density of 747.25 W kg−1, the maximum energy density of the assembled asymmetric supercapacitor assembled with Cu-PyAc-Am2Ac-Ni is 58.95 Wh kg−1 with cycling stability of 88.95 % after 5000 charges and discharges. This means that Cu-PyAc-Am2Ac-Ni is a promising electrode material for supercapacitors.

A new type of lanthanide–sodium metalloring organic framework featuring high proton conduction in a wide temperature range and detection of Fe3+ ions

The unprecedented octanuclear lanthanide–sodium metalloring cluster organic framework exhibits proton conductivity in a wide operating temperature range and sensitive sensing of iron ions.

Self-Assembly of Lanthanide-Aluminum Cluster-Organic Frameworks with Magnetocaloric Effect and Luminescence.

The self-assembly of the lanthanide metal-organic frameworks presents a formidable challenge but profound significance. Compared with the metal-organic frameworks based on 4f-3d ions, the chemistry of 4f-3p metal-organic frameworks has not been fully explored so far. In this study, two lanthanide-aluminum-based clusters [Ln6Al(IN)10(μ3-OH)5(μ3-O)3(H2O)8]·xH2O (x = 2, Ln = Gd, abbreviated as Gd6Al; x = 2.5, Ln = Eu, abbreviated as Eu6Al; HIN = isonicotinic acid) have been meticulously designed and obtained by hydrothermal reaction at low pH. The crystallographic study revealed that both Gd6Al and Eu6Al clusters exhibit an unprecedented sandwiched metal-organic framework holding a highly ordered honeycomb network. To our knowledge, it is the first case of Ln-Al-based cluster-organic frameworks. Furthermore, magnetic investigation of Gd6Al manifests a decent magnetic entropy change of -ΔSmmax = 28.8 J kg-1 K-1 at 2 K for ΔH = 7.0 T. Significantly, the introduction of AlIII ions into the lanthanide metal-organic frameworks displays excellent solid-state luminescent capability with a lifetime of 371.6 μs and quantum yield of 6.64%. The construction and investigation of these two Ln-Al clusters represent great progress in the 4f-3p metal-organic framework.

Pseudorotaxane Ligand‐Induced Formation of Copper(I) Iodide Cluster Based Assembly Materials: From Zero to Three Dimensional

Comprehensive SummaryIn this work, we have successfully obtained a series of novel copper(I)–iodide clusters (CuI NCs) based assembly materials by combining supramolecular pseudorotaxane ligands {[Mebpe+]PF6–@CB[6] (CB[6] = cucurbit[6]uril), L’·PF6} and linkers {BPHF@CB[6], [BPHF = C14H20N4(PF6)2], L·PF6}, including discrete cluster CuI 1 and extended cluster organic frameworks MORF 1 and MORF 2. CuI 1 can be described as a dumbbell‐shaped molecule with its body‐centered site and two vertexes respectively occupied by one [Cu5I6]– cluster and two CB[6] held together by two L’·PF6 ligands. The crystal structures of MORF 1 and MORF 2 are 1D anionic chain and four‐fold interpenetrated 3D cationic diamondoid structure, respectively, which all featured intriguing alternating CB[6] and CuI NCs. Furthermore, CuI 1 exhibits outstanding thermochromic and piezochromic luminescence. MORF 1 and MORF 2 also are detected pressure dependent luminescence properties with an enormous blue‐shift of the near‐infrared (NIR) emission band under high pressure compression. These exciting and smart materials possess great potential in the application field of novel temperature and pressure sensors.

A {Cu6}-added polyoxometalate cluster-organic framework: synthesis, structure and application as a solid support for enzyme immobilization.

A new two-dimensional {Cu6}-added polyoxometalate cluster-organic framework (Cu-POMCOF) was prepared by a hydrothermal method from lacunary polyoxoanions and was applied as a solid support for immobilizing MP-11 and Cyt c. The biocomposite complex exhibits higher stability and catalytic activity than the original free enzyme.

Self-assembly synthesis of Ru nanoparticles anchored on B, N co-doping carbon support for hydrogen evolution: Electronic state induced by the strong metal-support interactions

The strong metal-support interactions between metal and its support have been considered as an effective way to improve the electrocatalytic activity in heterogeneous catalysis, which can modulate metal d-band's energy level and, consequently, affect the adsorption/desorption of the intermediates on the metal nanoparticle's surface. In this paper, we use a self-assembly strategy for construction nano-sized Ru nanoparticles (NPs) anchored on B, N co-doping carbon nanorod carrier (Ru/BCN) as HER catalyst by using unique boron cluster-organic framework as precursor and self-sacrificing templates. This supramolecular framework forming with cucurbit [6]uril as the host and closo-[B12H12]2- as the guest can feature unique hexagonal nanorod morphology to confine the Ru NPs into framework through weak reductivity of closo-[B12H12]2-. After pyrolysis, the strong metal-support interactions between B, N co-doping carbon support (BCN) and Ru NPs have been found due to the synergistic coupling effect of co-dopants B and N, which can increase electron transfer between the metal nanoparticle and support. The overpotentials of 33 mV and 40 mV are required for as-prepared catalyst Ru/BCN to achieve a current density of 10 mA cm−2 in alkaline and acidic conditions, respectively, which are approximately one third of those of Ru/CN. These findings demonstrate that our synthetic way offers a potential route for fabricating co-doping carbon with B and N atoms to support Ru NPs with enhanced HER performance in pH-independent conditions.

Designed Syntheses of Three {Ni6PW9}-Based Polyoxometalates, from Isolated Cluster to Cluster-Organic Helical Chain.

Three new hexa-Ni-substituted Keggin-type polyoxometalates (POMs), [Ni6(OH)3- (DACH)3(H2O)6(PW9O34)]·31H2O (1), [Ni(DACH)2][Ni6(OH)3(DACH)3(HMIP)2(H2O)2(PW9O34)]·56 H2O (2), and [Ni(DACH)2][Ni6(OH)3(DACH)2(AP)(H2O)5(PW9O34)]·2H2O (3) (DACH = 1,2-Diami- nocyclohexane, MIP = 5-Methylisophthalate, AP = Adipate) were successfully made in the presence of DACH under hydrothermal conditions. 1 is an isolated hexa-Ni-substituted Keggin unit decorated by DACH. In order to further construct POM cluster-organic frameworks (POMCOFs) on the basis of 1, by analyzing the steric hindrances and orientations of the POM units, the rigid HMIP and flexible AP ligands were successively incorporated, and another anionic monomeric POM 2 and the new 1D POM cluster organic chain (POMCOC) 3 were obtained. HMIP ligand still acts as a decorating group on the Ni6 core of 2 but results in the different spatial arrangement of the {Ni6PW9} units. AP ligands in 3 successfully bridge adjacent isolated POM cluster units to 1D POMCOC with left-hand helices. The AP in 3 is the longest aliphatic carboxylic acid ligand in POMs, and the 1D POM cluster-AP helical chain represents the first 1D POMCOC with a helical feature.

Designing Cage-Supported Cluster-Organic Framework for Highly Efficient Optical Limiting

Designing Cage-Supported Cluster-Organic Framework for Highly Efficient Optical Limiting

Chiral {Ni6PW9} Cluster-Organic Framework: Synthesis, Structure, and Properties.

A chiral three-dimensional polyoxometalate cluster-organic framework (POMCOF) H3[(btc)Ni6(μ3-OH)3(H2O)5(B-α-PW9O34)]·17H2O (1, btc = 1,2,4-benzenetricarboxylate) has been made under hydrothermal conditions in the absence of amine or chiral starting reagents. 1 shows high stability in CH3CN/DMF (1:3), acidic, and basic solutions with the pH ranging from 2 to 12 for 5 days. The UV-vis reflectance spectra and Mott-Schottky measurements reveal that 1 could be a suitable catalyst for photocatalysis. Visible-light-driven H2 evolution studies have demonstrated that 1 is an ecofriendly, efficient, and recyclable catalyst with a H2 evolution rate of 1058.24 μmol h-1g-1. Nonlinear optical (NLO) measurement reveals that 1 exhibits a second-harmonic generation (SHG) response of about 1.4 times that of KH2PO4 (KDP), indicating that 1 is a potential NLO material as well.

Four Inorganic–Organic Hybrid Borates: From 2D Layers to 3D Oxoboron Cluster Organic Frameworks

Four inorganic-organic hybrid borates, K[B6O9(OH)(en)]·H2O (1, en = ethylenediamine), K[B6O9(OH)(1,3-dap)]·H2O (2, 1,3-dap = 1,3-diaminopropane), K[B6O9(OH)(1,6-dah)0.5]·H2O (3, 1,6-dah = 1,6-diaminlhexane) and [(1,3-dap)Cd@B5O8(OH)]·0.5H2O (4), were made under solvothermal conditions. 1 and 2 are isostructural and feature a 2D layer built by B6O9(OH) clusters and modified by en and 1,3-dap via B-N-C linkages. By replacing en and 1,3-dap with longer and more flexible 1,6-dah, a new type of oxoboron cluster organic framework 3 was obtained, which was composed of the same B6O9(OH) cluster layers as in 1 and 2 and 1,6-dah linkers. By replacing alkali metal K with transition metal Cd under similar synthetic conditions, another type of oxoboron cluster organic framework 4 was made in which the Cd-centered wheel cluster layers and 1,3-dap linkers were connected via Cd-N-C linkages.

Sn6 and Na4 Oxo Clusters Based Non-centrosymmetric Framework for Solution Iodine Absorption and Second Harmonic Generation Response.

A three-dimensional non-centrosymmetric cluster organic framework has successfully been built from the {Sn6} and {Na4} cluster units via the oxalate ligand, which belongs to the first 3D framework containing different cluster units in the field of tin-oxo clusters. Besides the interesting structural characteristics, the obtained 3D framework not only can efficiently adsorb the iodine molecules but also displays the second harmonic generation response under the 1064 nm Q-switch laser.

Luminescent cluster-organic frameworks constructed from predesigned supertetrahedral {Ln4Zn6} secondary building units.

3d-4f heterometallic supertetrahedral clusters with the formula of Ln4Zn6(μ6-O)L4(CH3COO)6(NO3)4(CH3OH)4(H2O)2 (1-Ln, Ln = Eu, Gd, Tb, H3L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol) have been successfully introduced as stable secondary building units (SBUs) to construct new cluster-organic frameworks with tunable emission, demonstrating a promising strategy for developing new optical materials.

Induced aggregation and synergistic coordination strategy in metal oxo clusters and their organic frameworks

The new class of materials of metal cluster organic framework (MCOFs) derive from metal organic framework (MOFs) and metal oxo clusters (MOCs). In recent years, MCOFs has attracted considerable attention for their combination of metal oxo clusters and porous characteristics. We herein summarize the progress of lanthanide cluster organic framework (LnCOFs), and point out the induced aggregation and synergetic coordination strategy. This strategy is suitable for making MCOFs and MOCs.

Copper(II) biocompatible coordination solids as potential platforms for diclofenac delivery systems

This study deals a new copper(II)-based cluster-organic framework, CUBA, targeted a matrix for diclofenac sodium delivery. CUBA was prepared by solvothermal reaction and characterized by several techniques. FEG-SEM data revealed presence of random porous over CUBA surface. BET equation fitting N2-adsorption isotherm showed a surface area and pore volume amount to ca. 55 ​m2 ​g-1 and 0.49 ​cm3 ​g-1, respectively. In vitro assays showed non-cytotoxic activity for CUBA in MRC-5 ​cell line. A microporous copper(II)-based metal-organic framework, herein labelled as BioMOF-Cu, was used as a comparison in drug load-releasing tests. CUBA exhibited encapsulation efficiency of 29.47, 36.74 and 60.72% at 2, 4 and 7 days, respectively, BioMOF-Cu showed 84.68% at 4 days. In PBS solution CUBA ranged at 13-18% of total drug-releasing at 72 ​h and BioMOF-Cu afforded 21% at 48 ​h. In vivo evaluation of the anti-inflammatory effects, CUBA and BioMOF-Cu decreased the paw edema when compared to the negative group.

Imidazole-induced self-assembly of polyoxovanadate cluster organic framework for efficient Knoevenagel condensation under mild conditions

Three new polyoxovanadates have been made, one of them displays highly efficient heterogeneous solvent-free catalytic activity and excellent recyclability in the Knoevenagel condensation at room temperature.

A polyoxometalate-encapsulated nanocage cluster organic framework built from {Cu4P2} units and its efficient bifunctional electrochemical performance.

The first polyoxometalate (POM)-encapsulated twenty-four-nucleus organophosphorus-copper nanocage cluster organic framework has been constructed. Here, the phosphomolybdate POMs were incorporated into an octahedral nanocage cluster organic framework, and the resulting material exhibited highly efficient bifunctional electrochemical performance. The crystalline material showed a high specific capacitance of 366.3 F g-1 at a current density of 3 A g-1.

The incorporation of heterovalent copper-oxo and copper-halide clusters for the fabrication of three porous cluster organic frameworks: syntheses, structures and iodine adsorption/release study

Three porous cluster organic frameworks constructed from the paddle-wheel Cu2(CO2)4 and cubane-like Cu4I4 clusters have been synthesized and characterized. Interestingly, compound 2 shows moderate gas uptake ability and I2 adsorption/release feature.

Construction of high-nuclear 4p–4f heterometallic {Ln11Ge12} cluster-organic frameworks with high-sensitivity luminescence sensing of Fe3+ in aqueous solution

The [Pr11Ge12] 4p–4f cluster-organic framework shows highly selective and sensitive sensing of Fe3+ in aqueous solution.

Construction of Two High-Nuclear 3d-4d Heterometallic Cluster Organic Frameworks by Introducing a Bifunctional Tripodal Alcohol as a Structure-Directing Agent.

Two unique heterometallic cluster organic frameworks, [Cd4 MnIII 4 MnII 6 (Tri)4 (CH3 COO)14 (μ4 -O)2 (μ3 -O)2 (H2 O)2 ] Cd(H2 O)2 ⋅9 H2 O (1) and Cu[Cd5 Cu6 (Tri)4 (CH3 COO)9 (H2 O)4 ]2 (CH3 COO)3 ⋅24 H2 O (2) (H3 Tri=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.