Kuil Mark, Puijk Iris M, Kleij Arjan W, Tooke Duncan M, Spek Anthony L, Reek Joost N H
Homogeneous and Supramolecular Catalysis, Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands.
Chem Asian J. 2009 Jan 5;4(1):50-7. doi: 10.1002/asia.200800147.
We report the assembly of supramolecular boxes and coordination polymers based on a rigid bis-zinc(II)-salphen complex and various ditopic nitrogen ligands. The use of the bis-zinc(II)-salphen building block in combination with small ditopic nitrogen ligands gave organic coordination polymers both in solution as well as in the solid state. Molecular modeling shows that supramolecular boxes with small internal cavities can be formed. However, the inability to accommodate solvent molecules (such as toluene) in these cavities explains why coordination polymers are prevailing over well-defined boxes, as it would lead to an energetically unfavorable vacuum. In contrast, for relatively longer ditopic nitrogen ligands, we observed the selective formation of supramolecular box assemblies in all cases studied. The approach can be easily extended to chiral analogues by using chiral ditopic nitrogen ligands.
我们报道了基于刚性双锌（II）-水杨醛缩邻氨基酚配合物和各种双齿氮配体的超分子盒和配位聚合物的组装。双锌（II）-水杨醛缩邻氨基酚结构单元与小的双齿氮配体结合使用，在溶液和固态中均得到了有机配位聚合物。分子模拟表明，可以形成具有小内腔的超分子盒。然而，这些腔内无法容纳溶剂分子（如甲苯）解释了为什么配位聚合物比明确界定的盒子更普遍，因为这会导致能量上不利的真空。相比之下，对于相对较长的双齿氮配体，在所有研究的情况下，我们都观察到了超分子盒组装体的选择性形成。通过使用手性双齿氮配体，该方法可以很容易地扩展到手性类似物。
