Molecular Conformation and Intermolecular Interactions in the Crystal Structures of Free-Base 5,15-Diarylporphyrins
详细信息 查看全文
- 作者：Andrew D. Bond ; Neil Feeder ; James E. Redman ; Simon J. Teat ; and Jeremy K. M. Sanders
- 刊名：Crystal Growth & Design
- 出版年：2002
- 出版时间：January 2002
- 年：2002
- 卷：2
- 期：1
- 页码：27 - 39
- 全文大小：691K
- 年卷期：v.2,no.1(January 2002)
- ISSN：1528-7505
文摘
Nine crystal structures of free-base 5,15-diarylporphyrin derivatives are reported, and systematicanalysis is made of the molecular conformations and intermolecular interactions in these and other comparablestructures. In all cases, the porphyrins show minimal out-of-plane distortion in the solid state, but significant in-plane distortion, consistent with previous observations. The simplest 5,15-diarylporphyrin (with no furthersubstitution on the macrocycle periphery) crystallizes as a solvate with features comparable to the structure ofporphine itself, and also in an unsolvated form in which edge-to-face interactions between the phenyl substituentand the porphyrin faces give rise to one-dimensional porphyrin chains. The majority of the structures reported hereare derived from a balance between these latter interactions and the common offset face-to-face 
-stacking interaction.Introduction of substituents such as hydroxyl and methoxy groups on the phenyl rings does not disrupt the edge-to-face interactions. Introduction of bulky groups on both sides of the phenyl substituent can disrupt chain formation,and the structures in these cases are dominated by offset -stacking. In structures where the porphyrins bearsolubilizing n-alkyl groups on the macrocycle periphery, the porphyrin chains generally may be considered to formlayers that are stacked with n-alkyl groups filling space between them.
-stacking interaction.Introduction of substituents such as hydroxyl and methoxy groups on the phenyl rings does not disrupt the edge-to-face interactions. Introduction of bulky groups on both sides of the phenyl substituent can disrupt chain formation,and the structures in these cases are dominated by offset -stacking. In structures where the porphyrins bearsolubilizing n-alkyl groups on the macrocycle periphery, the porphyrin chains generally may be considered to formlayers that are stacked with n-alkyl groups filling space between them.