Cincić Dominik, Friscić Tomislav, Jones William
Laboratory for General and Inorganic Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia.
J Am Chem Soc. 2008 Jun 18;130(24):7524-5. doi: 10.1021/ja801164v. Epub 2008 May 21.
A molecular-level mechanism is proposed for two cases of mechanochemical cocrystallization via halogen bonds. The proposed stepwise mechanism is based on the observation and structural characterization of intermediates that appear in early stages of the reaction. The mechanism arises from the competition of strong and weak intermolecular halogen bonds of the N...I and S...I type and involves the initial formation of finite molecular assemblies, held together via N...I bonds that subsequently polymerize into infinite chains by cross-linking through S...I bonds. This mechanism has been observed in the synthesis of linear as well as zigzag halogen-bonded chain architectures.
针对通过卤键进行机械化学共结晶的两种情况，提出了一种分子水平的机制。所提出的逐步机制基于对反应早期出现的中间体的观察和结构表征。该机制源于N...I和S...I型强分子间卤键与弱分子间卤键的竞争，涉及通过N...I键保持在一起的有限分子聚集体的初始形成，这些聚集体随后通过S...I键交联聚合成无限链。在合成线性以及锯齿形卤键链结构时已观察到这种机制。
