Engineering Solid-State Morphologies in Carbazole鈥揈thynylene Macrocycles
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- 作者：Aaron D. Finke ; Dustin E. Gross ; Amy Han ; Jeffrey S. Moore
- 刊名：Journal of the American Chemical Society
- 出版年：2011
- 出版时间：September 7, 2011
- 年：2011
- 卷：133
- 期：35
- 页码：14063-14070
- 全文大小：1221K
- 年卷期：v.133,no.35(September 7, 2011)
- ISSN：1520-5126
文摘
We present a crystallographic study that systematically investigates the effects of the n-alkyl side-chain length on the crystal packing in shape-persistent macrocycles. The solid-state packing of carbazole鈥揺thynylene-containing macrocycles is sensitive to the alkyl-chain length. In macrocycles containing n-alkyl side chains up to nine carbons in length, face-on aromatic 蟺 interactions predominate, while the addition of one carbon leads to a completely different packing arrangement. Macrocycles with C10 or C11 chains exhibit a novel packing motif wherein the alkyl chains intercalate between macrocycles, leading in one case to continuous solvent-filled channels. When crystals of the C10 macrocycle are bathed in solvent, the included molecules exchange with the external solvent, and the alkyl chain disorder changes in response to changes in the guest volume in order to retain crystallinity. Powder X-ray diffraction data indicate that alkyl鈥搈acrocycle interactions in the longer chains 鈥渆mulate鈥?the distances typical of face-to-face 蟺 interactions, leading to deceptive indicators of 蟺 stacking.