Organically-functionalised supertetrahedra as building blocks for hybrid materials

Building Blocks ◽

Organic Ligands ◽

Reaction Conditions ◽

Metal Centers ◽

Covalently Bonded ◽

Metal Organic ◽

Solvothermal Conditions

AbstractThe crystal structures of gallium sulfides prepared under solvothermal conditions, using 4-picoline as a solvent, are described. These materials contain [Ga10S16(NC6H7)4]2− clusters, in which the terminal S2− anions have been replaced by covalently bonded 4-picoline molecules. Whilst these phases contain isolated supertetrahedral clusters separated by organic moieties, linkage of such clusters via organic ligands is possible under suitable reaction conditions. These organically-functionalised supertetrahedra could therefore be used to design novel Metal-Organic frameworks (MOFs) in which the normally-encountered metal centers are replaced by supertetrahedral clusters.

Co(II)-based metal–organic framework induced apoptosis through kindling the HIF-1α/BNIP3 signaling pathway in microglial cells

Environmental Science Nano ◽

10.1039/d1en00719j ◽

2021 ◽

Author(s):

Xueting Yan ◽

Qundi Yang ◽

Xiaolong Fang ◽

Ping Xiong ◽

Shuang Liu ◽

...

Keyword(s):

Signaling Pathway ◽

Hybrid Materials ◽

Metal Clusters ◽

Metal Organic Framework ◽

Organic Ligands ◽

Microglial Cells ◽

Metal Organic ◽

Induced Apoptosis ◽

Organic Framework

Metal–organic frameworks (MOFs) are a rising class of porous hybrid materials constructed by coordination of metal clusters with organic ligands, which attract tremendous attention due to their superior properties. Although...

Selective Incorporation of Auxiliary Organic Ligands in Metal–Organic Frameworks Based on Twisted Π-Shaped Building Blocks

Crystal Growth & Design ◽

10.1021/cg200752v ◽

2011 ◽

Vol 11 (12) ◽

pp. 5167-5170 ◽

Cited By ~ 5

Author(s):

Hua Tian ◽

Kun Wang ◽

Qin-Xiang Jia ◽

Qian Sun ◽

Yu Ma ◽

...

Keyword(s):

Building Blocks ◽

Organic Ligands ◽

Selective Incorporation ◽

Metal Centers and Organic Ligands Determine Electrochemistry of Metal–Organic Frameworks

Small ◽

10.1002/smll.202106607 ◽

2022 ◽

pp. 2106607

Author(s):

Caoling Li ◽

Jian Shen ◽

Kangbing Wu ◽

Nianjun Yang

Keyword(s):

Organic Ligands ◽

Metal Centers ◽

Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

10.26434/chemrxiv.10316681.v1 ◽

2019 ◽

Author(s):

Andrew Rosen ◽

M. Rasel Mian ◽

Timur Islamoglu ◽

Haoyuan Chen ◽

Omar Farha ◽

...

Keyword(s):

Density Functional ◽

Redox Activity ◽

Screening Methods ◽

Bridging Ligands ◽

Metal Centers ◽

Computational Screening ◽

Open Metal Sites ◽

Metal Organic ◽

Unsaturated Metal Sites

Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O2 and N2 adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br-, μ-Cl-, μ-F-, μ-SH-, or μ-OH- groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O2 affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O2. In contrast with O2 adsorption, N2 adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V2+ open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl- ligands of M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH- groups would significantly enhance the strength of O2 adsorption at the open metal sites without a corresponding increase in the N2 affinity. Experimental investigation of Co2Cl2(BBTA) and Co2(OH)2(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O2 at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH- ligands and the presence of H-bonding interactions between the μ-OH- bridging ligands and the O2 adsorbate.

Two W/S/Cu-Cluster-Containing Metal–Organic Frameworks Fabricated by Multidentate Organic Ligands: New Topologies, Strong NLO Properties, and Efficient Luminescent Detection

Crystal Growth & Design ◽

10.1021/acs.cgd.0c01580 ◽

2021 ◽

Author(s):

Jinfang Zhang ◽

Qian Xiang ◽

Yuan Zhu ◽

Junyi Yang ◽

Yinglin Song ◽

...

Keyword(s):

Organic Ligands ◽

Nlo Properties ◽

Negative linear compressibility in nanoporous metal-organic frameworks rationalized by the empty channel structural mechanism

Physical Chemistry Chemical Physics ◽

10.1039/d1cp00214g ◽

2021 ◽

Author(s):

Francisco Colmenero

Keyword(s):

Crystal Structures ◽

Structural Mechanism ◽

Nanoporous Metal ◽

Metal Organic ◽

Linear Compressibility

Cobalt squarate hydroxide (Co3(C4O4)2(OH)2), zinc squarate tetrahydrate (ZnC4O4·4 H2O) and titanium oxalate trioxide dihydrate (Ti2(C2O4)O3·2 H2O) are nanoporous metal-organic frameworks possessing empty channels in their crystal structures. The crystal structures...

Lanthanide-Based Metal–Organic Frameworks Containing “V-Shaped” Tetracarboxylate Ligands: Synthesis, Crystal Structures, “Naked-Eye” Luminescent Detection, and Catalytic Properties

Inorganic Chemistry ◽

10.1021/acs.inorgchem.9b02177 ◽

2019 ◽

Vol 59 (1) ◽

pp. 264-273 ◽

Cited By ~ 11

Author(s):

Pengyan Wu ◽

Lingling Xia ◽

Mengjie Huangfu ◽

Fubin Fu ◽

Mengqiu Wang ◽

...

Keyword(s):

Crystal Structures ◽

Catalytic Properties ◽

Naked Eye ◽

Experimental investigations on the irregular synthesis of the iron(III) terephthalate metal-organic frameworks MOF-235 and MIL-101

Dalton Transactions ◽

10.1039/d0dt04341a ◽

2021 ◽

Author(s):

Isabelle Simonsson ◽

Philip Gärdhagen ◽

Moira Andrén ◽

Pui Lam Tam ◽

Zareen Abbas

Keyword(s):

Crystal Structures ◽

Experimental Investigations ◽

Surface Areas ◽

(Fe)-MOF-235 and (Fe)-MIL-101 are two well-studied iron(III) terephthalate metal-organic frameworks (MOFs) with dissimilar crystal structures and topologies. Previously reported syntheses of the former show greatly varying surface areas, indicating a...