Single Crystal to Single Crystal Polymerization of a Self-Assembled Diacetylene Macrocycle Affords Columnar Polydiacetylenes

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• 作者：Weiwei L. Xu ; Mark D. Smith ; Jeanette A. Krause ; Andrew B. Greytak ; Shuguo Ma ; Cory M. Read ; Linda S. Shimizu
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：March 5, 2014
• 年：2014
• 卷：14
• 期：3
• 页码：993-1002
• 全文大小：525K
• 年卷期：v.14,no.3(March 5, 2014)
• ISSN：1528-7505

文摘

This manuscript describes a single-crystal-to-single-crystal polymerization of the dihydrate of diacetylene 1 (1路2H₂O) to give an unusual polydiacetylene (PDA) structure that consists of aligned nanotubes, with each covalently bonded nanotube having two parallel PDA chains that run parallel down opposite sides of a channel defined by the macrocycle. Each PDA nanotube is connected with four other columns via amide hydrogen bonds with an N-(H)路路路O distance of 2.888(4) 脜. Such well-ordered polymers should display quasi-one-dimensional electronic structures and may be of interest for the formation of highly conductive organic materials. We obtained the 1路2H₂O form in bulk, which was polymerized by heating. Powder X-ray diffraction suggests that bulk PDA powder is single phase and displays a similar structure as the PDA single crystals. Furthermore, we showed that PDA crystals absorbed I₂ vapor. We believe that this unique PDA structure, which is amenable to property control via adsorbed guests, will be an attractive one for investigating charge-transfer doping in PDA-based organic electronic materials. We also observed two additional crystal forms, including 1路MeOH, which also shows a columnar assembly, and a tetrahydrate 1路4H₂O that shows water tetramers that link four cycles into a 2D sheet structure.