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Open AccessArticle

A Raman Spectroscopic and Computational Study of New Aromatic Pyrimidine-Based Halogen Bond Acceptors

1
Molecular Spectroscopy Laboratories, Department of Chemistry & Biochemistry, University of Mississippi, University, MS 38677, USA
2
Department of Chemistry, University of California, San Diego, La Jolla, CA 92093-0358, USA
*
Author to whom correspondence should be addressed.
Inorganics 2019, 7(10), 119; https://doi.org/10.3390/inorganics7100119
Received: 7 September 2019 / Revised: 25 September 2019 / Accepted: 27 September 2019 / Published: 2 October 2019
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
Two new aromatic pyrimidine-based derivatives designed specifically for halogen bond directed self-assembly are investigated through a combination of high-resolution Raman spectroscopy, X-ray crystallography, and computational quantum chemistry. The vibrational frequencies of these new molecular building blocks, pyrimidine capped with furan (PrmF) and thiophene (PrmT), are compared to those previously assigned for pyrimidine (Prm). The modifications affect only a select few of the normal modes of Prm, most noticeably its signature ring breathing mode, ν1. Structural analyses afforded by X-ray crystallography, and computed interaction energies from density functional theory computations indicate that, although weak hydrogen bonding (C–H···O or C–H···N interactions) is present in these pyrimidine-based solid-state co-crystals, halogen bonding and π-stacking interactions play more dominant roles in driving their molecular-assembly. View Full-Text
Keywords: halogen bonding; sigma–hole interactions; molecular recognition; self-assembly; supramolecular structures; crystal engineering; computational chemistry; supramolecular chemistry; vibrational spectroscopy; noncovalent interactions halogen bonding; sigma–hole interactions; molecular recognition; self-assembly; supramolecular structures; crystal engineering; computational chemistry; supramolecular chemistry; vibrational spectroscopy; noncovalent interactions
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MDPI and ACS Style

Hardin, A.E.S.; Ellington, T.L.; Nguyen, S.T.; Rheingold, A.L.; Tschumper, G.S.; Watkins, D.L.; Hammer, N.I. A Raman Spectroscopic and Computational Study of New Aromatic Pyrimidine-Based Halogen Bond Acceptors. Inorganics 2019, 7, 119.

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