Remote Stabilization of Copper Paddlewheel Based Molecular Building Blocks in Metal–Organic Frameworks

Gao, Wen; Cai, Rong; Pham, Tony; Forrest, Katherine A.; Hogan, Adam; Nugent, Patrick; Williams, Kia; Wojtas, Łukasz; Luebke, Ryan; Weseliński, Łukasz J.; Zaworotko, Michael J.; Space, Brian; Chen, Yu‐Sheng; Eddaoudi, Mohamed; Shi, Xiaodong; Ma, Shengqian

doi:10.1021/acs.chemmater.5b00084

Cited by 75 publications

(64 citation statements)

References 83 publications

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“…[1] Nonetheless,water or acidic/ alkaline aqueous solutions remain am ajor barrier impeding MOFs in many practical areas because of damage to their pristine structures when encountering various environmental or industrial conditions. [3] Notwithstanding,i ti sa lso highly desirable to develop and investigate different paths to generate aqueous stable MOFs particularly under aw ide range of pH conditions. [3] Notwithstanding,i ti sa lso highly desirable to develop and investigate different paths to generate aqueous stable MOFs particularly under aw ide range of pH conditions.…”

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A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

et al. 2018

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A majority of metal-organic frameworks (MOFs) fail to preserve their physical and chemical properties after exposure to acidic, neutral, or alkaline aqueous solutions, therefore limiting their practical applications in many areas. The strategy demonstrated herein is the design and synthesis of an organic ligand that behaves as a buffer to drastically boost the aqueous stability of a porous MOF (JUC-1000), which maintains its structural integrity at low and high pH values. The local buffer environment resulting from the weak acid-base pairs of the custom-designed organic ligand also greatly facilitates the performance of JUC-1000 in the chemical fixation of carbon dioxide under ambient conditions, outperforming a series of benchmark catalysts.

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A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

et al. 2018

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“…[2] In general, the crystalline MOFs are often sustained by solventg uests that are included within the pores. [4][5][6][7][8][9] Someo fthes trategies to impart permanent porosity includem ultiple coordination bondst hrough metalc luster secondary building units (SBUs), [4] use of rigid organic linkers, [5,6] network interpenetration, [7] incorporation of certain functional groups in organicl inkers, [8] size-matching ligand braces that reinforce the integrities of structures, [9] etc. Permanent porosity is thus as erious concern, and it must be ensured for successful applicationo fM OFs.T he robustnesso fM OFs allows one to fine-tunet he size as well as chemical and functional nature of the pores and also carry out postsynthetic modifications (PSM).…”

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Robust MOFs of “tsg” Topology Based on Trigonal Prismatic Organic and Metal Cluster SBUs: Single Crystal to Single Crystal Postsynthetic Metal Exchange and Selective CO₂ Capture

Chandrasekhar

Savitha

Moorthy

2017

Chemistry A European J

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The self-assembly of a rigid and trigonal prismatic triptycene-hexaacid H THA with Co(NO ) or Mn(NO ) leads to isostructural metal-organic frameworks (MOFs) that are sustained by 6-connecting metal cluster [M (μ -O)(COO) ] secondary building units (SBUs). The Co- and Mn-MOFs, constructed from organic and metal-cluster building blocks that are both trigonal prismatic, correspond to the heretofore unknown "tsg" topology. Due to the rigidity and concave attributes of H THA, the networks in the Co- and Mn-MOFs are highly porous and undergo 3-fold interpenetration. The interpenetration imparts permanent microporosity and high thermal stability to the MOFs to permit postsynthetic metal exchange (PSME) and gas sorption. The PSME occurs in a single crystal to single crystal fashion when the crystals of Co- or Mn-MOFs are immersed in a solution of Cu(NO ) in MeOH/H O. Further, the isostructural robust MOFs exhibit significant gas sorption and remarkable selectivity for CO over N (ca. 100 fold) at ambient conditions. In fact, the postsynthetically-engineered Cu-THA exhibits better CO sorption than Co-THA and Mn-THA. A composite of effects that include pore dimensions (ca. 0.7 nm), unsaturated metal centers, and basic environments conferred by the quinoxaline nitrogen atoms appears to be responsible for the observed high CO capture and selectivity. The high symmetry and structural attributes of the organic linker seemingly dictate adoption of the trigonal-prismatic metal cluster SBU by the metal ions in the MOFs.

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“…[2,40] Ah ighly successful platform of MOFs that has been synthesized are the (3,24)-connected rht-MOFs. [68] This MOF,k nown as MPAF-1 (MPAF standsf or metalpyrazolate framework) or rht-MOF-pyr,e xhibits as imilarsurface area, pore volume, and free volume as rht-MOF-1, but displays am uch highers tabilityi nw ater,m oisture, steam, and acid. The overall structure of rht-MOFs is characterized by having 24 edges of ac uboctahedron connectingw ith ah exatopic ligand having C 3 symmetry.M oreover, the overall framework of rht-MOFs consists of three distinct cages:c uboctahedron, truncated tetrahedron, and truncated octahedron (see FigureS1, Supporting Information, SI).…”

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“…[9, These MOFs are synthesized with hexatopicl igands consisting of three coplanar isophthalatem oieties that are coordinated to [M 2 (O 2 CR) 4 ] square paddlewheel clusters. [68] Although the aforementioned MOFs are examples of rht-MOFs that were synthesized using the Cu 3 Ot rimer units, [56,68] many other rht-MOFsh ave been constructed such that it avoids the utilization of such moieties. rht-MOFs are ap romising platform of MOFs because they exhibit very high surfacea reas, contain open-metal sites, and have tunable pores and functionality.…”

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“…[68] This MOF,k nown as MPAF-1 (MPAF standsf or metalpyrazolate framework) or rht-MOF-pyr,e xhibits as imilarsurface area, pore volume, and free volume as rht-MOF-1, but displays am uch highers tabilityi nw ater,m oisture, steam, and acid. [68] This MOF,k nown as MPAF-1 (MPAF standsf or metalpyrazolate framework) or rht-MOF-pyr,e xhibits as imilarsurface area, pore volume, and free volume as rht-MOF-1, but displays am uch highers tabilityi nw ater,m oisture, steam, and acid.…”

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Theoretical Insights into the Tuning of Metal Binding Sites of Paddlewheels in rht‐Metal–Organic Frameworks

et al. 2015

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Theoretical investigations of CO2 sorption are performed in four members of the highly tunable rht-metal-organic framework (MOF) platform. rht-MOFs contain two Cu(2+) ions that comprise the metal paddlewheels and both are in chemically distinct environments. Indeed, one type of Cu(2+) ion faces toward the center of the linker whereas the other type faces away from the center of the linker. Electronic structure calculations on the series of rht-MOFs demonstrate that one of the Cu(2+) ions has a consistently higher charge magnitude relative to the other. As a consequence, the Cu(2+) ion with the higher partial positive charge acts as the favored sorbate binding site at initial loading as revealed by grand canonical Monte Carlo (GCMC) simulations that include many-body polarization. It was found that the charge distribution about the copper paddlewheels is dependent on the type of functional groups present on the linker. This study demonstrates how the binding site about the metal paddlewheels in the rht-MOF platform can be controlled by changing the functionality on the organic ligand.

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Remote Stabilization of Copper Paddlewheel Based Molecular Building Blocks in Metal–Organic Frameworks

Cited by 75 publications

References 83 publications

A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

Robust MOFs of “tsg” Topology Based on Trigonal Prismatic Organic and Metal Cluster SBUs: Single Crystal to Single Crystal Postsynthetic Metal Exchange and Selective CO₂ Capture

Theoretical Insights into the Tuning of Metal Binding Sites of Paddlewheels in rht‐Metal–Organic Frameworks

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Remote Stabilization of Copper Paddlewheel Based Molecular Building Blocks in Metal–Organic Frameworks

Cited by 75 publications

References 83 publications

A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation

Robust MOFs of “tsg” Topology Based on Trigonal Prismatic Organic and Metal Cluster SBUs: Single Crystal to Single Crystal Postsynthetic Metal Exchange and Selective CO2 Capture

Theoretical Insights into the Tuning of Metal Binding Sites of Paddlewheels in rht‐Metal–Organic Frameworks

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Robust MOFs of “tsg” Topology Based on Trigonal Prismatic Organic and Metal Cluster SBUs: Single Crystal to Single Crystal Postsynthetic Metal Exchange and Selective CO₂ Capture