Using hinged ligands to target structurally flexible copper(II) MOFs

Witold M. Bloch; Christian J. Doonan; Christopher J. Sumby

doi:10.1039/c3ce41244j

Using hinged ligands to target structurally flexible copper(II) MOFs

Witold M. Bloch, Christian J. Doonan, Christopher J. Sumby

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

Abstract

Here we report two new flexible MOFs based on a bis-pyrazolylmethane 'hinged' link design that favours the formation of two distinct structural nodes within the resulting 2-D and 3-D structures. The less sterically demanding ligand H₂bcppm affords a 2-D layered MOF, {Cu₂[Cu ^II(NO₃)₂(bcppm)₂](DMF) ₂}·2DMF (1), constructed from copper(ii) paddlewheel and mononuclear octahedral copper(ii) nodes. The use of a more sterically encumbered tetramethyl analogue H₂bcpdmpm induces a dramatic twisting of the ligand backbone that yields a 3-D MOF{Cu₄[Cu^I(bcpdmpm) ₂]₂(EtOH)₂(H₂O)₂}(NO ₃)₂·12DMF (2) formed from a very similar mix of nodes, specifically copper(ii) paddlewheel clusters and mononuclear tetrahedrally coordinated copper(i) centres. Herein we describe the crystal structures, solid-state flexibility, and gas adsorption properties of both materials.

Original language	English
Pages (from-to)	9663-9671
Number of pages	9
Journal	CrystEngComm
Volume	15
Issue number	45
DOIs	https://doi.org/10.1039/c3ce41244j
Publication status	Published - 7 Dec 2013
Externally published	Yes

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title = "Using hinged ligands to target structurally flexible copper(II) MOFs",

abstract = "Here we report two new flexible MOFs based on a bis-pyrazolylmethane 'hinged' link design that favours the formation of two distinct structural nodes within the resulting 2-D and 3-D structures. The less sterically demanding ligand H2bcppm affords a 2-D layered MOF, {Cu2[Cu II(NO3)2(bcppm)2](DMF) 2}·2DMF (1), constructed from copper(ii) paddlewheel and mononuclear octahedral copper(ii) nodes. The use of a more sterically encumbered tetramethyl analogue H2bcpdmpm induces a dramatic twisting of the ligand backbone that yields a 3-D MOF{Cu4[CuI(bcpdmpm) 2]2(EtOH)2(H2O)2}(NO 3)2·12DMF (2) formed from a very similar mix of nodes, specifically copper(ii) paddlewheel clusters and mononuclear tetrahedrally coordinated copper(i) centres. Herein we describe the crystal structures, solid-state flexibility, and gas adsorption properties of both materials.",

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AU - Bloch, Witold M.

AU - Doonan, Christian J.

AU - Sumby, Christopher J.

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N2 - Here we report two new flexible MOFs based on a bis-pyrazolylmethane 'hinged' link design that favours the formation of two distinct structural nodes within the resulting 2-D and 3-D structures. The less sterically demanding ligand H2bcppm affords a 2-D layered MOF, {Cu2[Cu II(NO3)2(bcppm)2](DMF) 2}·2DMF (1), constructed from copper(ii) paddlewheel and mononuclear octahedral copper(ii) nodes. The use of a more sterically encumbered tetramethyl analogue H2bcpdmpm induces a dramatic twisting of the ligand backbone that yields a 3-D MOF{Cu4[CuI(bcpdmpm) 2]2(EtOH)2(H2O)2}(NO 3)2·12DMF (2) formed from a very similar mix of nodes, specifically copper(ii) paddlewheel clusters and mononuclear tetrahedrally coordinated copper(i) centres. Herein we describe the crystal structures, solid-state flexibility, and gas adsorption properties of both materials.

AB - Here we report two new flexible MOFs based on a bis-pyrazolylmethane 'hinged' link design that favours the formation of two distinct structural nodes within the resulting 2-D and 3-D structures. The less sterically demanding ligand H2bcppm affords a 2-D layered MOF, {Cu2[Cu II(NO3)2(bcppm)2](DMF) 2}·2DMF (1), constructed from copper(ii) paddlewheel and mononuclear octahedral copper(ii) nodes. The use of a more sterically encumbered tetramethyl analogue H2bcpdmpm induces a dramatic twisting of the ligand backbone that yields a 3-D MOF{Cu4[CuI(bcpdmpm) 2]2(EtOH)2(H2O)2}(NO 3)2·12DMF (2) formed from a very similar mix of nodes, specifically copper(ii) paddlewheel clusters and mononuclear tetrahedrally coordinated copper(i) centres. Herein we describe the crystal structures, solid-state flexibility, and gas adsorption properties of both materials.

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JO - CrystEngComm

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Using hinged ligands to target structurally flexible copper(II) MOFs

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