pH Dependent Formation of Unprecedented Water–Bromide Cluster in the Bromide Salts of PTP Assisted by Anion?π Interactions: Synthesis, Structure, and DFT Study

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• 作者：Prankrishna Manna ; Saikat Kumar Seth ; Antonio Bauzá ; Monojit Mitra ; Somnath Ray Choudhury ; Antonio Frontera ; Subrata Mukhopadhyay
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：February 5, 2014
• 年：2014
• 卷：14
• 期：2
• 页码：747-755
• 全文大小：479K
• ISSN：1528-7505

文摘

Two new terpyridine derivatives [PTPH₃](Br)₃路3H₂O (1) and [PTPH₃](Br₃)(Br)₂路H₂O (2), (PTP = 4鈥?(4-pyridyl)-2,2鈥?6鈥?2鈥?terpyridine) were synthesized and characterized by single crystal X-ray diffraction analyses. In 1, intricate combination of anion路路路蟺/蟺鈥撓€/蟺路路路anion interactions generates the supramolecular network while 2 exhibits a combination of two different anion路路路蟺/蟺鈥撓€/蟺路路路anion and anion路路路蟺路路路anion assemblies. As anticipated, both of them are interlinked through hydrogen bonds affording molecular networks, but surprisingly, 1 shows hydrate aggregation and interactions with anions to generate water鈥揵romide cluster blends in the solid lattices. A search of the crystal structure database (CSD) yielded only eight hits presenting an infinite tape in the solid state structure formed by bromide anions and water molecules, none of which had similar distribution of bromide and water as observed in 1. Interestingly, in compound 1, the bromide anion is involved in the formation of anion鈥搘ater cluster and also engaged in anion路路路蟺 interactions, thus generating a unique cluster of water鈥揳nion/anion路路路蟺/蟺鈥撓€/蟺路路路anion/anion鈥搘ater cluster network. The different networks have been investigated by means of DFT calculations and the interactions characterized using the Bader鈥檚 theory of 鈥渁toms-in-molecules鈥?