The Synthesis of Organic Molecules of Intrinsic Microporosity Designed to Frustrate Efficient Molecular Packing

Efficient reactions between fluorine‐functionalised biphenyl and terphenyl derivatives with catechol‐functionalised terminal groups provide a route to large, discrete organic molecules of intrinsic microporosity (OMIMs) that provide porous solids solely by their inefficient packing. By altering the...

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Bibliographic Details
Published in:Chemistry : a European journal 2016-02, Vol.22 (7), p.2466-2472
Main Authors: Taylor, Rupert G. D., Bezzu, C. Grazia, Carta, Mariolino, Msayib, Kadhum J., Walker, Jonathan, Short, Rhys, Kariuki, Benson M., McKeown, Neil B.
Format: Article
Language:English
Subjects:
adsorption
aromatic nucleophilic substitution
Biphenyl
Catechol
Chemical synthesis
Chemistry
Derivatives
Fluorine
Hydrocarbons
Microporosity
microporous materials
Molecular chains
molecular packing
Organic chemistry
Packing
Porosity
Simulation
Surface area
Terminals
triptycene
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Summary:Efficient reactions between fluorine‐functionalised biphenyl and terphenyl derivatives with catechol‐functionalised terminal groups provide a route to large, discrete organic molecules of intrinsic microporosity (OMIMs) that provide porous solids solely by their inefficient packing. By altering the size and substituent bulk of the terminal groups, a number of soluble compounds with apparent BET surface areas in excess of 600 m2 g−1 are produced. The efficiency of OMIM structural units for generating microporosity is in the order: propellane>triptycene>hexaphenylbenzene>spirobifluorene>naphthyl=phenyl. The introduction of bulky hydrocarbon substituents significantly enhances microporosity by further reducing packing efficiency. These results are consistent with findings from previously reported packing simulation studies. The introduction of methyl groups at the bridgehead position of triptycene units reduces intrinsic microporosity. This is presumably due to their internal position within the OMIM structure so that they occupy space, but unlike peripheral substituents they do not contribute to the generation of free volume by inefficient packing. Poor packing, packed porosity: Organic molecules of intrinsic microporosity (OMIMs) are large, discrete molecules that provide porous solids solely by their inefficient packing. By altering the number, size, and bulk of the terminal groups, a number of OMIMs with apparent BET surface areas in excess of 600 m2 g−1 are produced.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201504212