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

Inorganics

DavitaL. Watkins¹  ThomasL. Ellington¹  ArnoldL. Rheingold¹  NathanI. Hammer²  SuongT. Nguyen³  AprilE. S. Hardin³  GregoryS. Tschumper³ 

[1] Biochemistry, University of Mississippi, University, MS 38677, USA;Department of Chemistry, University of California, San Diego, La Jolla, CA 92093-0358, USA;;Molecular Spectroscopy Laboratories, Department of Chemistry &

关键词: halogen bonding;    sigma–hole interactions;    molecular recognition;    self-assembly;    supramolecular structures;    crystal engineering;    computational chemistry;    supramolecular chemistry;    vibrational spectroscopy;    noncovalent interactions;   

DOI  :  10.3390/inorganics7100119

来源: DOAJ

【 摘 要 】

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.

【 授权许可】

Unknown