- Two New Solvent-modulated Zinc(II) Metal-Organic Hybrid Materials based on Rigid Tripodal Carboxylate Ligand and 2,2′-Bipy Co-ligand: Crystal Structures and Luminescent Properties
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The zinc(II) coordination polymers [Zn(Htatb)(2,2′-bipy)·(NMP)·H2O] (1) and [Zn3(tatb)2(2,2′-bipy)3·H2O] (2) (H3tatb = 4,4′,4′′-s-triazine-2,4,6-triyl-tribenzoic acid; 2,2′-bipy = 2,2′-bipyridyl, NMP = N-methyl-2-pyrrolidon), were synthesized hydrothermally, and characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Both compounds 1 and 2 possess expectant low dimensional coordination structures, which further connected into interesting 3D networks by hydrogen bond and strong π-π interactions. Moreover, the thermal stabilities and fluorescent properties of 1 and 2 were investigated.
- Liu, Xiao-Bin,Xiao, Zhen-Yu,Zhang, Ming-Hui,Zhang, Liang-Liang,Wang, Rong-Ming,Sun, Dao-Feng
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- Electrochemically Mediated Syntheses of Titanium(III)-Based Metal-Organic Frameworks
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Although metal-organic frameworks featuring coordinatively unsaturated transition metal sites are relatively common, examples with redox-active cations are rare. In this report, we describe the electrochemically mediated synthesis of TiIII-MIL-101 from the inexpensive Ti4+ precursor TiCl4. The framework obtained via electrosynthesis is identical to that prepared from the significantly more expensive and air-sensitive starting material TiCl3. The above electrosynthetic strategy was also extended to prepare TiIII-MIL-100 and two high-quality extended TiIII-MIL structures, for the first time. These materials represent examples of titanium-based MOFs with extended pore structures. Several physical methods demonstrate that these materials are superior in quality to samples of the analogous MOFs prepared via conventional routes from starting exogenous TiCl3. Given the ease with which the electrosyntheses may be carried out and their compatibility with a broad range of bridging ligands, we expect that this new methodology will find utility for the synthesis of a number of novel materials containing coordinatively unsaturated, redox-active metal cations.
- Antonio, Alexandra M.,Rosenthal, Joel,Bloch, Eric D.
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- Synthesis, characterization, and photoluminescence of isostructural Mn, Co, and Zn MOFs having a diamondoid structure with large tetrahedral cages and high thermal stability
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Three novel Mn, Co, and Zn MOFs containing large tetrahedral cages have been prepared and are stable up to 400 °C; X-ray diffraction revealed the frameworks are isostructural having a diamondoid structure of "hourglass" subunits connected by triangular carboxylate ligands. The Royal Society of Chemistry 2005.
- Sun, Daofeng,Ma, Shengqian,Ke, Yanxiong,Petersen, Tracy M.,Zhou, Hong-Cai
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- Record Complexity in the Polycatenation of Three Porous Hydrogen-Bonded Organic Frameworks with Stepwise Adsorption Behaviors
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Hydrogen-bonded organic frameworks (HOFs) show great potential in many applications, but few structure-property correlations have been explored in this field. In this work, we report that self-assembly of a rigid and planar ligand gives rise to flat hexagonal honeycomb motifs which are extended into undulated two-dimensional (2D) layers and finally generate three polycatenated HOFs with record complexity. This kind of undulation is absent in the 2D layers built from a very similar but nonplanar ligand, indicating that a slight torsion of ligand produces overwhelming structural change. This change delivers materials with unique stepwise adsorption behaviors under a certain pressure originating from the movement between mutually interwoven hexagonal networks. Meanwhile, high chemical stability, phase transformation, and preferential adsorption of aromatic compounds were observed in these HOFs. The results presented in this work would help us to understand the self-assembly behaviors of HOFs and shed light on the rational design of HOF materials for practical applications.
- Li, Yu-Lin,Alexandrov, Eugeny V.,Yin, Qi,Li, Lan,Fang, Zhi-Bin,Yuan, Wenbing,Proserpio, Davide M.,Liu, Tian-Fu
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- An interweaving MOF with high hydrogen uptake
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An interweaving copper metal-organic framework possessing high porosity and high hydrogen uptake has been successfully designed and synthesized. Copyright
- Sun, Daofeng,Ma, Shengqian,Ke, Yanxiong,Collins, David J.,Zhou, Hong-Cai
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- Synthesis, Structures, and Fluorescent Properties of Three Cobalt-Based Coordination Polymers with a Rigid Tripodal Carboxylate Ligand
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Three cobalt(II) coordination polymers, [Co2(tatb)2(2,2′-bipy)2 (H2O)2·DMA·2H2O] (1), [Co2(tatb)2(1,10-phen)2(H2O)2·2H2O] (2) and [Co(tatb)(1,3-dpp)·H2O] (3) (H3tatb = 4,4′,4;″-(1,3,5-triazine-2,4,6-triyl)tribenzoic acid; 2,2′-bipy = 2,2′-bipyridyl; 1,10-phen = 1,10-phenanthroline; 1,3-dpp = 1,3-bis(pyridin-4-yl)propane), were synthesized solvothermally and characterized by single-crystal and powder X-ray diffraction (PXRD), as well as IR spectroscopy. Complexes 1 and 2 exhibit 1D double-chain structures, which further connect into interesting 3D networks by hydrogen bond and strong π-π interactions. Complex 3 possesses 2D 44-sql topology, which is packed parallel in an AA fashion. Moreover, thermal stability properties and photoluminescence properties of 1, 2 and 3 were also investigated.
- Liu, Xiao-Bin,Xiao, Zhen-Yu,Huang, Ao,Wang, Wen,Zhang, Liang-Liang,Wang, Rong-Ming,Sun, Dao-Feng
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- Two novel 3D-MOFs (Ca-TATB and Co-HKUST): Synthesis, structure and characterization
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We report X-ray crystallographic investigations of two novel metal–organic frameworks (MOFs) by using 4,4′,4′'-s-triazine-2,4,6-triyltribenzoic acid [H3TATB] ligand with Ca metal for 1 and 1,3,5 benzene tri-carboxylic acid [H3BTC] ligand with Co metal for 2 respectively. The compound [Ca6(TATB)4(H2O)(DMA)4] (1); (where DMA = dimethylacetamide); was successfully synthesized in a sealed tube at 110 °C for 72 h and shows the formation of a 3D network with embedded 1D channels which are occupied by solvent molecules. The structure of the compound 1 is relatively new and its structural differences with the reported Cu-TATB compounds are noteworthy. The compound Co-HKUST (2) was synthesized by solvothermal method at 140 °C for 72 h. Paddlewheel secondary building units are used to construct Co-HKUST (2) which is isostructural analogue of HKUST-1 enriching the series which consists of Cr, Fe, Ni, Zn, Mo, and Ru analogues. Both 1 and 2 are metastable MOFs characterized by complementary techniques namely powder X-ray diffraction and FTIR analysis.
- Marri, Subba R.,Chauhan, Neha,Tiwari, Ranjay K.,Kumar, Jitendra,Behera
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- Perovskite Quantum Dots Encapsulated in a Mesoporous Metal-Organic Framework as Synergistic Photocathode Materials
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Metal halide perovskite quantum dots, with high light-absorption coefficients and tunable electronic properties, have been widely studied as optoelectronic materials, but their applications in photocatalysis are hindered by their insufficient stability because of the oxidation and agglomeration under light, heat, and atmospheric conditions. To address this challenge, herein, we encapsulated CsPbBr3 nanocrystals into a stable iron-based metal-organic framework (MOF) with mesoporous cages (～5.5 and 4.2 nm) via a sequential deposition route to obtain a perovskite-MOF composite material, CsPbBr3@PCN-333(Fe), in which CsPbBr3 nanocrystals were stabilized from aggregation or leaching by the confinement effect of MOF cages. The monodispersed CsPbBr3 nanocrystals (4-5 nm) within the MOF lattice were directly observed by transmission electron microscopy and corresponding mapping analysis and further confirmed by powder X-ray diffraction, infrared spectroscopy, and N2 adsorption characterizations. Density functional theory calculations further suggested a significant interfacial charge transfer from CsPbBr3 quantum dots to PCN-333(Fe), which is ideal for photocatalysis. The CsPbBr3@PCN-333(Fe) composite exhibited excellent and stable oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic activities in aprotic systems. Furthermore, CsPbBr3@PCN-333(Fe) composite worked as the synergistic photocathode in the photoassisted Li-O2 battery, where CsPbBr3 and PCN-333(Fe) acted as optical antennas and ORR/OER catalytic sites, respectively. The CsPbBr3@PCN-333(Fe) photocathode showed lower overpotential and better cycling stability compared to CsPbBr3 nanocrystals or PCN-333(Fe), highlighting the synergy between CsPbBr3 and PCN-333(Fe) in the composite.
- Chen, Xiao,Guan, Dehui,Qiao, Guan-Yu,Qin, Jun-Sheng,Rao, Heng,Wang, Jia-Ao,Xu, Ji-Jing,Yu, Jihong,Yuan, Shuai
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supporting information
p. 14253 - 14260
(2021/09/13)
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- Tuning the Structure and Hydrolysis Stability of Calcium Metal-Organic Frameworks through Integrating Carboxylic/Phosphinic/Phosphonic Groups in Building Blocks
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Crystal structure and hydrolysis stability are fundamentally important for the application of metal-organic frameworks (MOFs) in biotechnology. Herein, five novel 3-D MOFs, built up from biocompatible calcium ions and ligands containing carboxylic, phosphinic, or phosphonic coordinating groups, have been solvothermally synthesized, and their crystal structures were determined by single-crystal X-ray diffraction. Their hydrolysis stability study demonstrated that the water stability of these Ca-based MOFs can be tuned by integrating carboxylic/phosphinic/phosphonic coordinating groups in building blocks.
- Sun, Jing,Huang, Tao,Yin, Qi,Li, Lan,Liu, Tian-Fu,Huang, Xin-Song,Cao, Rong
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p. 8021 - 8027
(2020/12/02)
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- IL-induced formation of dynamic complex iodide anions in IL?MOF composites for efficient iodine capture
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Highly efficient capture of radioactive iodine from vapor or solvent remains a serious task for nuclear waste disposal and environmental protection, for which the development of excellent adsorbents is of great importance. Herein, a new strategy named IL-induced formation of dynamic complex iodide anions in IL?MOF composites was developed to prepare efficient iodine capture adsorbents. The IL?PCN-333(Al) composite shows record iodine adsorption capacities of 7.35 g g-1 and 3.4 g g-1 for iodine vapor and solution, respectively. The mechanism study reveals that complex iodide anions can be dynamically formed by the reaction of bromide ions in the IL and iodine molecules, which have strong electrostatic interactions with the imidazolium cations of the IL. Owing to the reversibility of the polyiodide formation, the IL?PCN-333(Al) also shows excellent recyclable performance. This work provides a general methodology for intensification of the interactions of neutral molecules and host materials that may find applications in various adsorption-based separation processes.
- Tang, Yuanzhe,Huang, Hongliang,Li, Jian,Xue, Wenjuan,Zhong, Chongli
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supporting information
p. 18324 - 18329
(2019/08/12)
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- Photocatalytic Hydrogen Production Coupled with Selective Benzylamine Oxidation over MOF Composites
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Photocatalytic water splitting requires separation of the mixed H2 and O2 products and is often hampered by the sluggish O2-producing half reaction. An approach is now reported to address these issues by coupling the H2-producing half reaction with value-added benzylamine oxidation reaction using metal–organic framework (MOF) composites. Upon MOF photoexcitation, the electrons rapidly reduce the protons to generate H2 and the holes promote considerable benzylamine oxidation to N-benzylbenzaldimine with high selectivity. Further experimental characterizations and theoretical calculation reveal that the highly conjugated s-triazine strut in the MOF structure is crucial to the efficient charge separation and excellent photocatalytic activity.
- Liu, Hang,Xu, Caiyun,Li, Dandan,Jiang, Hai-Long
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supporting information
p. 5379 - 5383
(2018/04/02)
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- Star-shaped fluorescent liquid crystals derived from s-triazine and 1,3,4-oxadiazole moieties
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Star-shaped molecules with a central triazine core appended with three 1,3,4-oxadiazole arms have been designed with the variation in the number, length and pattern of peripheral chain substitution. These compounds were investigated for their thermal, electrochemical and photophysical behavior. These nonconventional molecules stabilized wide range columnar phases and demonstrated how one can tune the liquid crystal self-assembly through simple structural modification. The photophysical properties of these star shaped molecules are extremely dependent on the number and pattern of peripheral chain substitution. These compounds exhibit blue and green luminescence in the solid/liquid crystal state. The ability to overcome aggregation induced quenching is due to the favorable packing of these molecules in the solid state. These solid-state emissive materials with good thermal stability and lower band gap may find applications in the construction of emissive displays and organic lasers.
- Pradhan, Balaram,Pathak, Suraj Kumar,Gupta, Ravindra Kumar,Gupta, Monika,Pal, Santanu Kumar,Achalkumar, Ammathnadu S.
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supporting information
p. 6117 - 6130
(2016/07/06)
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- Structure-assisted functional anchor implantation in robust metal-organic frameworks with ultralarge pores
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A facile functionalization assisted by the structural attributes of PCN-333 has been studied while maintaining the integrity of the parent MOF including ultralarge pores, chemical robustness, and crystallinity. Herein we thoroughly analyzed ligand exchange phenomena in PCN-333 and demonstrate that the extent of exchange can be tailored by varying the exchange conditions as potential applications may require. Through this method a variety of functional groups are incorporated into PCN-333. To further show the capabilities of this system introduction of a BODIPY fluorophore as a secondary functionality was performed to the functionalized framework via a click reaction. We anticipate the PCN-333 with functional anchor can serve as a stable platform for further chemistry to be explored in future applications.
- Park, Jihye,Feng, Dawei,Zhou, Hong-Cai
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supporting information
p. 1663 - 1672
(2015/02/19)
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- Dual Exchange in PCN-333: A Facile Strategy to Chemically Robust Mesoporous Chromium Metal-Organic Framework with Functional Groups
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A facile preparation of a mesoporous Cr-MOF, PCN-333(Cr) with functional group, has been demonstrated through a dual exchange strategy, involving a sequential ligand exchange and metal metathesis process. After optimization of the exchange system, the functionalized PCN-333(Cr), N3-PCN-333(Cr) shows well maintained crystallinity, porosity, as well as much improved chemical stability. Because of the exceptionally large pores (～5.5 nm) in PCN-333(Cr), a secondary functional moiety, Zn-TEPP with a size of 18 ? × 18 ?, has been successfully clicked into the framework. In this article, we have also analyzed kinetics and thermodynamics during dual exchange process, showing our attempts to interpret the exchange event in the PCN-333. Our findings not only provide a highly stable mesoporous Cr-MOF platform for expanding MOF-based applications, but also suggest a route to functionalized Cr-MOF which may have not been achievable through conventional approaches.
- Park, Jihye,Feng, Dawei,Zhou, Hong-Cai
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supporting information
p. 11801 - 11809
(2015/09/28)
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- Microporous, tetraarylethylene-based polymer networks generated in a reductive polyolefination process
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Microporous Polymer Networks (MPNs) that contain aggregate-induced emission (AIE) active tetraphenylethylene (TPE) or other tetraarylethylene units have been generated in a reductive polyolefination process starting from four different tris(α,α-dichlorobenzyl)arene derivatives with dicobalt octacarbonyl or chromium(ii)acetate as reductive olefination agents. Microporosity with moderately high BET surface areas up to 500 m2 g-1 could be combined with high solid state photoluminescence quantum yields up to 25.3% for polymer network P4. This unique combination should be promising for applications as optical solid state sensors, especially for MPNs with electron-deficient triazine core units.
- Preis,Dong,Brunklaus,Scherf
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supporting information
p. 1582 - 1587
(2015/04/27)
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- A highly stable zeotype mesoporous zirconium metal-organic framework with ultralarge pores
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Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8 nm and the highest pore volume of 2.8 cm3 g-1among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN- 777 and different guests can be varied to realize efficient immobilization.
- Feng, Dawei,Wang, Kecheng,Liu, Tian-Fu,Park, Jihye,Wei, Zhangwen,Bosch, Mathieu,Zhou, Hong-Cai,Su, Jie,Zou, Xiaodong,Yakovenko, Andrey
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supporting information
p. 149 - 154
(2015/08/19)
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- Chromium Metal Organic Frameworks and Synthesis of Metal Organic Frameworks
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The present invention relates to monocrystalline metal organic frameworks comprising chromium ions and carboxylate ligands and the use of the same, for example their use for storing a gas. The invention also relates to methods for preparing metal organic frameworks comprising chromium, titanium or iron ions and carboxylate ligands. The methods of the invention allow such metal organic frameworks to be prepared in monocrystalline or polycrystalline forms.
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