Structural diversity in metal-organic frameworks built from rigid tetrahedral [Si(p- C6H4CO2)4] 4- struts

Robert P. Davies; Rob Less; Paul D. Lickiss; Karen Robertson; Andrew J. P. White

doi:10.1021/cg1008768

Structural diversity in metal-organic frameworks built from rigid tetrahedral [Si(p- C₆H₄CO₂)₄] ⁴- struts

Robert P. Davies, Rob Less, Paul D. Lickiss, Karen Robertson, Andrew J. P. White

Department of Chemistry

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

74 Citations (SciVal)

Abstract

The silicon-based connector [Si(p-C₆H₄CO ₂)₄]^4- (L) has been employed in the construction of six new metal-organic framework (MOF) materials, all of which have been characterized by single crystal X-ray diffraction techniques. The isostructural frameworks [Cd₂(L)(H₂O)₂] •(DMA) and [Mn₂(L)(H₂O)₂]•(DMA) _2.5, IMP-8Cd and IMP-8Mn, respectively, contain extended [M(CO ₂)₂]_n chains, often termed rod SBUs (secondary building units), which are cross-linked into a 3D network by tetrahedral L struts to give microporous networks. In contrast, [Cu₂(L)(H ₂O)₂]•(DMA)₁₂ (IMP-9) contains dinuclear paddle-wheel Cu₂(CO₂)₄ SBUs connected together with L struts to give an overall PtS type net. [Me₂NH ₂]₂[Cd₃(L)₂(H₂O) ₂]•(DMA)₈(H₂O)₈, [Me ₂NH₂]₂[Zn₃(L)₂] •(DMF)₆, and [Me₂NH₂]₂[Zn ₃(L)₂]•(DMF)₃ (IMP-10, IMP-11, and IMP-12, respectively) all contain anionic 3D frameworks which are charge balanced by the presence of dimethylammonium cations within their pores. These dimethylammonium cations arise from the hydrolysis of DMA or DMF, or they can be introduced directly by addition of [Me₂NH₂]Cl. IMP-10, IMP-11, and IMP-12 all contain trinuclear octacoordinate SBU nodes, although subtle differences in the geometry of these SBUs result in the formation of different network topologies in each case. Examples of MOFs containing rigid tetrahedral carboxylate connectors are currently uncommon, and several previously unobserved topologies are introduced in this study.

Original language	English
Pages (from-to)	4571-4581
Number of pages	11
Journal	Crystal Growth and Design
Volume	10
Issue number	10
DOIs	https://doi.org/10.1021/cg1008768
Publication status	Published - 6 Oct 2010

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10.1021/cg1008768

http://dx.doi.org/10.1021/cg1008768

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@article{b4d23ad5f6b94c568d6d500e1c197dde,

title = "Structural diversity in metal-organic frameworks built from rigid tetrahedral [Si(p- C6H4CO2)4] 4- struts",

abstract = "The silicon-based connector [Si(p-C6H4CO 2)4]4- (L) has been employed in the construction of six new metal-organic framework (MOF) materials, all of which have been characterized by single crystal X-ray diffraction techniques. The isostructural frameworks [Cd2(L)(H2O)2] •(DMA) and [Mn2(L)(H2O)2]•(DMA) 2.5, IMP-8Cd and IMP-8Mn, respectively, contain extended [M(CO 2)2]n chains, often termed rod SBUs (secondary building units), which are cross-linked into a 3D network by tetrahedral L struts to give microporous networks. In contrast, [Cu2(L)(H 2O)2]•(DMA)12 (IMP-9) contains dinuclear paddle-wheel Cu2(CO2)4 SBUs connected together with L struts to give an overall PtS type net. [Me2NH 2]2[Cd3(L)2(H2O) 2]•(DMA)8(H2O)8, [Me 2NH2]2[Zn3(L)2] •(DMF)6, and [Me2NH2]2[Zn 3(L)2]•(DMF)3 (IMP-10, IMP-11, and IMP-12, respectively) all contain anionic 3D frameworks which are charge balanced by the presence of dimethylammonium cations within their pores. These dimethylammonium cations arise from the hydrolysis of DMA or DMF, or they can be introduced directly by addition of [Me2NH2]Cl. IMP-10, IMP-11, and IMP-12 all contain trinuclear octacoordinate SBU nodes, although subtle differences in the geometry of these SBUs result in the formation of different network topologies in each case. Examples of MOFs containing rigid tetrahedral carboxylate connectors are currently uncommon, and several previously unobserved topologies are introduced in this study. ",

author = "Davies, \{Robert P.\} and Rob Less and Lickiss, \{Paul D.\} and Karen Robertson and White, \{Andrew J. P.\}",

year = "2010",

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doi = "10.1021/cg1008768",

language = "English",

volume = "10",

pages = "4571--4581",

journal = "Crystal Growth and Design",

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T1 - Structural diversity in metal-organic frameworks built from rigid tetrahedral [Si(p- C6H4CO2)4] 4- struts

AU - Davies, Robert P.

AU - Less, Rob

AU - Lickiss, Paul D.

AU - Robertson, Karen

AU - White, Andrew J. P.

PY - 2010/10/6

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N2 - The silicon-based connector [Si(p-C6H4CO 2)4]4- (L) has been employed in the construction of six new metal-organic framework (MOF) materials, all of which have been characterized by single crystal X-ray diffraction techniques. The isostructural frameworks [Cd2(L)(H2O)2] •(DMA) and [Mn2(L)(H2O)2]•(DMA) 2.5, IMP-8Cd and IMP-8Mn, respectively, contain extended [M(CO 2)2]n chains, often termed rod SBUs (secondary building units), which are cross-linked into a 3D network by tetrahedral L struts to give microporous networks. In contrast, [Cu2(L)(H 2O)2]•(DMA)12 (IMP-9) contains dinuclear paddle-wheel Cu2(CO2)4 SBUs connected together with L struts to give an overall PtS type net. [Me2NH 2]2[Cd3(L)2(H2O) 2]•(DMA)8(H2O)8, [Me 2NH2]2[Zn3(L)2] •(DMF)6, and [Me2NH2]2[Zn 3(L)2]•(DMF)3 (IMP-10, IMP-11, and IMP-12, respectively) all contain anionic 3D frameworks which are charge balanced by the presence of dimethylammonium cations within their pores. These dimethylammonium cations arise from the hydrolysis of DMA or DMF, or they can be introduced directly by addition of [Me2NH2]Cl. IMP-10, IMP-11, and IMP-12 all contain trinuclear octacoordinate SBU nodes, although subtle differences in the geometry of these SBUs result in the formation of different network topologies in each case. Examples of MOFs containing rigid tetrahedral carboxylate connectors are currently uncommon, and several previously unobserved topologies are introduced in this study.

AB - The silicon-based connector [Si(p-C6H4CO 2)4]4- (L) has been employed in the construction of six new metal-organic framework (MOF) materials, all of which have been characterized by single crystal X-ray diffraction techniques. The isostructural frameworks [Cd2(L)(H2O)2] •(DMA) and [Mn2(L)(H2O)2]•(DMA) 2.5, IMP-8Cd and IMP-8Mn, respectively, contain extended [M(CO 2)2]n chains, often termed rod SBUs (secondary building units), which are cross-linked into a 3D network by tetrahedral L struts to give microporous networks. In contrast, [Cu2(L)(H 2O)2]•(DMA)12 (IMP-9) contains dinuclear paddle-wheel Cu2(CO2)4 SBUs connected together with L struts to give an overall PtS type net. [Me2NH 2]2[Cd3(L)2(H2O) 2]•(DMA)8(H2O)8, [Me 2NH2]2[Zn3(L)2] •(DMF)6, and [Me2NH2]2[Zn 3(L)2]•(DMF)3 (IMP-10, IMP-11, and IMP-12, respectively) all contain anionic 3D frameworks which are charge balanced by the presence of dimethylammonium cations within their pores. These dimethylammonium cations arise from the hydrolysis of DMA or DMF, or they can be introduced directly by addition of [Me2NH2]Cl. IMP-10, IMP-11, and IMP-12 all contain trinuclear octacoordinate SBU nodes, although subtle differences in the geometry of these SBUs result in the formation of different network topologies in each case. Examples of MOFs containing rigid tetrahedral carboxylate connectors are currently uncommon, and several previously unobserved topologies are introduced in this study.

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UR - http://dx.doi.org/10.1021/cg1008768

U2 - 10.1021/cg1008768

DO - 10.1021/cg1008768

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JF - Crystal Growth and Design

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ER -

Structural diversity in metal-organic frameworks built from rigid tetrahedral [Si(p- C₆H₄CO₂)₄] ⁴- struts

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