Jiang Ji-Jun, Zheng Sheng-Run, Liu Yu, Pan Mei, Wang Wei, Su Cheng-Yong
MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Inorg Chem. 2008 Nov 17;47(22):10692-9. doi: 10.1021/ic801516b. Epub 2008 Oct 16.
The synergistic interplay of coordination and hydrogen-bonding interactions leads to assembly of isomorphous compounds of the general formula [Ln(ntb) 2](ClO 4) 3.(BDA4BPy) 3.2MeCN} infinity (Ln = La, Sm and Pr, ntb = tris(2-benzimidazoylmethyl)amine, and BDA4BPy = N (1), N (4)-bis(pyridin-4-ylmethylene)-benzene-1,4-diamine), of which polymorphic crystals can be isolated in a different solvent system. In acetonitrile (MeCN) solution, the compounds crystallize as a red color (Ln = La, meso -1, Ln = Pr, meso -2), while in an acetonitrile-benzonitrile (MeCN-PhCN) mixture, yellow crystals are obtained (Ln = Pr, helical - 2). The single-crystal X-ray diffraction analyses of these crystals reveal that the structures display similar cylindrical arrays containing polycompartmental cavities for guest inclusion. Occurrence of polymorphism is due to formation of helical and meso-helical arrays, giving rise to a way to tune the helicity through the solvent effects on the helix propensity of the bis-tripodal coordination converters.
配位和氢键相互作用的协同作用导致通式为Ln(ntb)₂₃·(BDA4BPy)₃·2MeCN}∞（Ln = La、Sm和Pr，ntb = 三(2 - 苯并咪唑基亚甲基)胺，BDA4BPy = N(1),N(4) - 双(吡啶 - 4 - 基亚甲基) - 苯 - 1,4 - 二胺）的同构化合物的组装，其中多晶型晶体可在不同的溶剂体系中分离得到。在乙腈（MeCN）溶液中，这些化合物结晶为红色（Ln = La，内消旋 - 1，Ln = Pr，内消旋 - 2），而在乙腈 - 苯甲腈（MeCN - PhCN）混合物中，则得到黄色晶体（Ln = Pr，螺旋 - 2）。对这些晶体进行的单晶X射线衍射分析表明，其结构呈现出类似的圆柱形阵列，包含用于客体包合的多隔室空腔。多晶型现象的出现是由于形成了螺旋和中螺旋阵列，从而提供了一种通过溶剂对双三脚架配位转换器螺旋倾向的影响来调节螺旋度的方法。
