Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation
dc.contributor.author | Dutta, Ananya | en_US |
dc.contributor.author | Koh, Kyoungmoo | en_US |
dc.contributor.author | Wong‐foy, Antek G. | en_US |
dc.contributor.author | Matzger, Adam J. | en_US |
dc.date.accessioned | 2015-04-02T15:12:04Z | |
dc.date.available | 2016-05-10T20:26:28Z | en |
dc.date.issued | 2015-03-23 | en_US |
dc.identifier.citation | Dutta, Ananya; Koh, Kyoungmoo; Wong‐foy, Antek G. ; Matzger, Adam J. (2015). "Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation." Angewandte Chemie International Edition 54(13): 3983-3987. | en_US |
dc.identifier.issn | 1433-7851 | en_US |
dc.identifier.issn | 1521-3773 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/110813 | |
dc.description.abstract | Design and synthesis of porous solids employing both reversible coordination chemistry and reversible covalent bond formation is described. The combination of two different linkage modes in a single material presents a link between two distinct classes of porous materials as exemplified by metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). This strategy, in addition to being a compelling material‐discovery method, also offers a platform for developing a fundamental understanding of the factors influencing the competing modes of assembly. We also demonstrate that even temporary formation of reversible connections between components may be leveraged to make new phases thus offering design routes to polymorphic frameworks. Moreover, this approach has the striking potential of providing a rich landscape of structurally complex materials from commercially available or readily accessible feedstocks.Teamwork saves the day when coordination chemistry and covalent bond formation can both occur in a single material. A balance between the incubation time of the organic components and solvent decomposition/base formation governs the competition between the two processes and determines the phase outcome. Even the temporary formation of reversible connections between components can be leveraged to make new phases. | en_US |
dc.publisher | WILEY‐VCH Verlag | en_US |
dc.subject.other | metal–organic frameworks | en_US |
dc.subject.other | coordination modes | en_US |
dc.subject.other | covalent organic frameworks | en_US |
dc.subject.other | crystal engineering | en_US |
dc.subject.other | microporous materials | en_US |
dc.title | Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation | en_US |
dc.type | Article | en_US |
dc.rights.robots | IndexNoFollow | en_US |
dc.subject.hlbsecondlevel | Chemistry | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109 (USA) | en_US |
dc.contributor.affiliationum | Department of Macromolecular Science and Engineering, University of Michigan, Ann Arbor, MI 48109 (USA) | en_US |
dc.contributor.affiliationother | Current address: The Dow Chemical Company, Core R&D, Midland, MI 48674 (USA) | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/110813/1/anie_201411735_sm_miscellaneous_information.pdf | |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/110813/2/3983_ftp.pdf | |
dc.identifier.doi | 10.1002/anie.201411735 | en_US |
dc.identifier.source | Angewandte Chemie International Edition | en_US |
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dc.identifier.citedreference | In this context it should be noted that in situ ligand formation from irreversible covalent coupling in tandem with coordination chemistry has been demonstrated. See for example: D. Zhao, D. Yuan, A. Yakovenko, H.‐C. Zhou, Chem. Commun. 2010, 46, 4196 – 4199. | en_US |
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dc.identifier.citedreference | A role for diethylamine as a competitive species for imine formation cannot be ruled out as an additional contributing factor. | en_US |
dc.identifier.citedreference | To our knowledge, ketimine COFs are absent from the literature. | en_US |
dc.identifier.citedreference | As we have noted elsewhere, and in contrast to its misuse in the field, such framework materials must not be termed “polymorphs”. Polymorphs have a strict isomeric relationship that is not easily satisfied in porous material containing varying degrees of solvation. This fact motivates the use of the present term “polymorphic frameworks”. The distinction is critical because, for example, stability ordering of polymorphic framework materials is expected to be solvent dependent whereas this is forbidden for true polymorphs. In fact, the closest molecular analogy is in solvate stability where solvate inclusion engenders relative stability relationships that can depend strongly on solvent and temperature. In molecular compounds such relationships are sometimes termed “pseudopolymorphic”. Thus by this logic the different topologies of coordination polymers could be considered to be pseudopolymorphs. However, such a term is esoteric and subject to debate even within the small‐molecule community and so “polymorphic framework” is preferred. | en_US |
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dc.owningcollname | Interdisciplinary and Peer-Reviewed |
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