Copper(I) Coordination Polymers of N,N鈥?Bis[3-(methylthio)propyl]pyromellitic Diimide: Crystal Transformation and Solvatochromism by Halogen鈭捪€ Interactions

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• 作者：Garam Park ; Hojin Yang ; Tae Ho Kim ; Jineun Kim
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：February 7, 2011
• 年：2011
• 卷：50
• 期：3
• 页码：961-968
• 全文大小：1179K
• 年卷期：v.50,no.3(February 7, 2011)
• ISSN：1520-510X

文摘

Four copper(I) coordination polymers with ligand N,N鈥?bis[3-(methylthio)propyl]pyromellitic diimide (L), [Cu₂I₂L₂]_n (1), [Cu₂I₂L₂]_n (2), [Cu₂I₂L]_n (3), and {[Cu₂I₂L₂]路CH₂Cl₂}_n (4), have been successfully synthesized and structurally characterized by single-crystal X-ray diffraction. Structural transformations between the polymers were controlled by the appropriate solvent composition, mole ratio, or temperature. When a 1:1 CuI/L ratio was employed, dimorphic products, 1 and 2, based on a rhomboid Cu₂I₂ cluster were obtained from an acetonitrile solution and from a dichloromethane/acetonitrile solution with ultrasonication, respectively. When a 1:2 CuI/L ratio was employed, polymer 3 based on infinite stair-step polymer (CuI)_{鈭?/sub> was crystallized. Crystalline product 4 was obtained by the transformation of 1 in a mixed-solvent system with a 1:5 acetonitrile/dichloromethane ratio. Polymers 1鈭?b>4 were transformed into polymer 3 at 197 掳C. X-ray structures of 2鈭?b>4 show short distances (3.406鈭?.667 脜) between halogens (I^{鈭?/sup> and Cl) and aromatic rings. 1 and 4 show solvatochromism; upon inclusion of the colorless electron donor CH2Cl2, the red color changes as a result of the formation of a chloride鈭捪€ charge-transfer complex 4 of a pale-colored electron acceptor, 1. Therefore, the origin of the red color from 2 and 3 is also assigned as iodide-to-electron-deficient aromatic 蟺 charge transfer.}}