Coordinating Benzenes Stack Stronger than Noncoordinating Benzenes, even at Large Horizontal Displacements

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• 作者：Dušan P. Malenov ; Jovan Lj. Dragelj ; Goran V. Janjić ; S. D. Zarić
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：August 3, 2016
• 年：2016
• 卷：16
• 期：8
• 页码：4169-4172
• 全文大小：321K
• 年卷期：0
• ISSN：1528-7505

文摘

Stacking interactions between two benzene molecules that coordinate transition metal ions within organometallic sandwich and half-sandwich compounds were investigated by performing Cambridge Structural Database (CSD) search and DFT-D calculations. Calculations of interaction energies revealed that stacking interactions between coordinating benzenes of sandwich (−3.69 kcal/mol) and half-sandwich compounds (−3.29 kcal/mol) are significantly stronger than the stacking interaction between noncoordinating benzenes (−2.73 kcal/mol). At large horizontal displacements (offset r = 5.0 Å), these sandwich∥sandwich interactions are remarkably strong (−3.03 kcal/mol), while half-sandwich∥half-sandwich interactions are significantly weaker (−1.27 kcal/mol). The results of calculations are in good agreement with the data in the crystal structures from the CSD, where 76% of sandwich∥sandwich contacts have large horizontal displacements, which is significantly more than 46% of half-sandwich∥half-sandwich contacts arranged in this fashion. The study provides valuable information about interactions of aromatic molecules relevant to crystal engineering, materials design, and molecular recognition.