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Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Cocrystal Monolayers

Sacchi, M, Brewer, AY, Jenkins, SJ, Parker, JE, Friščić, T and Clarke, SM (2013) Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Cocrystal Monolayers Langmuir: the ACS journal of surfaces and colloids, 29 (48). pp. 14903-14911.

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This work describes the combined use of synchrotron X-ray diffraction and density functional theory (DFT) calculations to understand the cocrystal formation or phase separation in 2D monolayers capable of halogen bonding. The solid monolayer structure of 1,4-diiodobenzene (DIB) has been determined by X-ray synchrotron diffraction. The mixing behavior of DIB with 4,4′-bipyridyl (BPY) has also been studied and interestingly is found to phase-separate rather than form a cocrystal, as observed in the bulk. DFT calculations are used to establish the underlying origin of this interesting behavior. The DFT calculations are demonstrated to agree well with the recently proposed monolayer structure for the cocrystal of BPY and 1,4-diiodotetrafluorobenzene (DITFB) (the perfluorinated analogue of DIB), where halogen bonding has also been identified by diffraction. Here we have calculated an estimate of the halogen bond strength by DFT calculations for the DITFB/BPY cocrystal monolayer, which is found to be ∼20 kJ/mol. Computationally, we find that the nonfluorinated DIB and BPY are not expected to form a halogen-bonded cocrystal in a 2D layer; for this pair of species, phase separation of the components is calculated to be lower energy, in good agreement with the diffraction results.

Item Type: Article
Subjects : Chemistry
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
Sacchi, M
Brewer, AY
Jenkins, SJ
Parker, JE
Friščić, T
Clarke, SM
Date : 11 November 2013
DOI : 10.1021/la402910a
Copyright Disclaimer : © 2013 American Chemical Society. This work is licensed under the Creative Commons Attribution 4.0 International License.
Depositing User : Symplectic Elements
Date Deposited : 10 Mar 2017 10:51
Last Modified : 31 Oct 2017 19:11

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