Unraveling interactions in molecular crystals using dispersion corrected density functional theory : the case of the epoxydihydroarsanthrene molecules

Download
  1. Get@NRC: Unraveling interactions in molecular crystals using dispersion corrected density functional theory : the case of the epoxydihydroarsanthrene molecules (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1021/ct500832g
AuthorSearch for: ; Search for: ; Search for: ; Search for:
TypeArticle
Journal titleJournal of Chemical Theory and Computation
ISSN1549-9618
Volume10
Issue11
Pages50105019; # of pages: 10
AbstractNoncovalent interactions are prevalent in crystal packing and supramolecular chemistry. Directional noncovalent interactions such as donor-acceptor bonds (e.g., hydrogen, chalcogen, and pnictogen bonds) as well as nondirectional forces (such as dispersion) come together to stabilize supramolecular assemblies by striking a delicate energetic balance. Typically, a two-pronged approach employing experimental X-ray structures and gas phase quantum chemical modeling has been used to understand and design supramolecular architectures. Drawing from recent advances in molecular crystal modeling with dispersion corrected density functional theory (DFT), we propose in this article a combination of qualitative noncovalent index (NCI) analysis and periodic and gas phase DFT calculations on substitutional crystal analogues to unravel the dominant interactions in a particular crystal packing. We illustrate the possibilities of this approach by studying three crystal packings of epoxydihydroarsanthrene analogues that present a complex combination of donor-acceptor interactions including pnictogen-pnictogen, pnictogen-π, and pnictogen-chalcogen. We show that, in these crystals, the chalcogen-pnictogen interaction dominates over the pnictogen-pnictogen and pnictogen-π. In the latter, the role of donor and acceptor is reversed depending on the interacting moieties. Multiple chalcogen-pnictogen interactions necessitate larger donor atoms, such as sulfur. These observations explain and rationalize the experimentally observed crystal structures.
Publication date
LanguageEnglish
AffiliationSecurity and Disruptive Technologies; National Research Council Canada
Peer reviewedYes
NPARC number21272795
Export citationExport as RIS
Report a correctionReport a correction
Record identifierd61a9e08-cc7f-4050-8a75-74a12e2eccd5
Record created2014-12-03
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)