Cooperative Effects and Optimal Halogen Bonding Motifs for Self-Assembling Systems

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• 作者：Xin Cindy Yan ; Patric Schyman ; William L. Jorgensen
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：April 17, 2014
• 年：2014
• 卷：118
• 期：15
• 页码：2820-2826
• 全文大小：344K
• 年卷期：v.118,no.15(April 17, 2014)
• ISSN：1520-5215

文摘

Halogen bonding, due to its directionality and tunable strength, is being increasingly utilized in self-assembling materials and crystal engineering. Using density functional theory (DFT) and molecular mechanics (OPLS/CM1Ax) calculations, multiply halogen bonded complexes of brominated imidazole and pyridine are investigated along with their potential in construction of self-assembling architectures. Dimers with 1鈥?0 halogen bonds are considered and reveal maximal binding energies of 3鈥?6 kcal/mol. Cooperative (nonadditive) effects are found in complexes that extend both along and perpendicular to the halogen bonding axes, with interaction energies depending on polarization, secondary interactions, and ring spacers. Four structural motifs were identified to yield optimal halogen bonding. For the largest systems, the excellent agreement found between the DFT and OPLS/CM1Ax results supports the utility of the latter approach for analysis and design of self-assembling supramolecular structures.