Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers.
Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers.
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DOI：
10.1107/s2052252515000147
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发表时间：
2015-03-01
期刊：
影响因子：
3.9
通讯作者：
Brammer L
中科院分区：
文献类型：
--
作者：
Wright JS;Vitórica-Yrezábal IJ;Adams H;Thompson SP;Hill AH;Brammer L
研究了一类小分子芳烃（甲苯、二甲苯）与Ag（I）配位聚合物的结构转变。这项研究突出了在这些转变的汽-固相互作用和预组织在固态中的作用。合成了一类一维配位聚合物[Ag 4（O2 C（CF2）2CF 3）4（phenazine）2（arene）n]·m（arene），1（arene =甲苯或二甲苯），并对其进行了晶体学表征.芳烃客体损失引起结构转变，产生一对多晶型配位聚合物[Ag 4（O2 C（CF 2）2CF 3）4（吩嗪）2]，2a和/或2b，分别具有一维和二维结构。探讨了1的聚合物链在形成多晶型物的选择性中的预组织作用，并且还证明了甲苯和对二甲苯在形成含芳烃结构1中对邻二甲苯或间二甲苯的模板作用。无芳烃相2b的形成，不能通过其他方法以相纯的形式获得，被证明是从1-tol·tol [Ag 4（O2 C（CF2）2CF 3）4（吩嗪）2（甲苯）]·2（甲苯）损失甲苯的唯一产物，该相含有以不寻常的μ：η1，η1方式与Ag（I）配位的甲苯。还探索了多晶型配位聚合物之间的溶剂蒸气辅助转化以及溶剂蒸气对配位聚合物1至2a和2b的转化的影响。的转换已被检查和确认的X-射线衍射，核磁共振光谱和热分析，包括在原位衍射研究的一些转变。
The structural transformations of a family of coordination polymers that entrap small arenes (toluene, xylene) by Ag(I) coordination has been investigated. The study highlights the role in these transformations of vapour–solid interactions and pre-organization in the solid state. A family of one-dimensional coordination polymers, [Ag4(O2C(CF2)2CF3)4(phenazine)2(arene)n]·m(arene), 1 (arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2], 2a and/or 2b, with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of 1 in the selectivity for formation of either polymorph is explored, and the templating effect of toluene and p-xylene over o-xylene or m-xylene in the formation of arene-containing architecture 1 is also demonstrated. The formation of arene-free phase 2b, not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from 1-tol·tol [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η1,η1 manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers 1 to 2a and 2b is also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, including in situ diffraction studies of some transformations.