Liu Guang-Ning, Jiang Xiao-Ming, Fan Qing-Shun, Hussain Muhammad Bilal, Li Ke, Sun Hui, Li Xin-Yu, Liu Wan-Qing, Li Cuncheng
Key Laboratory of Chemical Sensing & Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan , Jinan, Shandong 250022, P. R. China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, P. R. China.
Inorg Chem. 2017 Feb 20;56(4):1906-1918. doi: 10.1021/acs.inorgchem.6b02478. Epub 2017 Feb 7.
In situ alkylation or protonation reactions on the thiazolyl-N donors of benzothiazole (btz) and its derivative 2-aminobenzothiazole (abtz) occurred to form four structure directing agents (SDAs), which feature different structure directing abilities and hydrophobicities. The thiazolyl-N alkylated and protonated btz cations direct to form an α-type (AgI) iodoargentate chain in (Etbtz)(AgI) (1), (Prbtz)(AgI) (2), and (Hbtz)(AgI) (3), respectively, while the thiazolyl-N protonated abtz cation directs to form a new type of (AgI) anionic chain in (Habtz)(AgI) (4). Compounds 1 and 4 represent the first noncentrosymmetric (NCS) hybrid iodoargentates with organic S-containing N-heterocycle derivative cations as SDAs. Further, 1 exhibits high water stability and is second harmonic generation (SHG) active with a response about twice that of KDP (KHPO). Importantly, the water stability studies indicate that hybrid iodoargentates with hydrophobic N-alkylated SDAs are more stable in water than those with relative hydrophilic N-protonated SDAs.
在苯并噻唑（btz）及其衍生物2-氨基苯并噻唑（abtz）的噻唑基-N供体上发生原位烷基化或质子化反应，形成了四种结构导向剂（SDA），它们具有不同的结构导向能力和疏水性。噻唑基-N烷基化和质子化的btz阳离子分别在（Etbtz）（AgI）（1）、（Prbtz）（AgI）（2）和（Hbtz）（AgI）（3）中导向形成α型（AgI）碘银酸盐链，而噻唑基-N质子化的abtz阳离子在（Habtz）（AgI）（4）中导向形成一种新型的（AgI）阴离子链。化合物1和4代表了首例以含硫有机N杂环衍生物阳离子作为SDA的非中心对称（NCS）杂化碘银酸盐。此外，1表现出高水稳定性，并且具有二次谐波产生（SHG）活性，其响应约为KDP（KHPO）的两倍。重要的是，水稳定性研究表明，具有疏水性N-烷基化SDA的杂化碘银酸盐在水中比具有相对亲水性N-质子化SDA的杂化碘银酸盐更稳定。
