Cangelosi Virginia M, Zakharov Lev N, Fontenot Sean A, Pitt Melanie A, Johnson Darren W
Department of Chemistry and Materials Science Institute, University of Oregon, Oregon Nanoscience and Microtechnologies Institute (ONAMI), Eugene, OR 97403-1253, USA.
Dalton Trans. 2008 Jul 14(26):3447-53. doi: 10.1039/b802178c. Epub 2008 Apr 18.
The reaction of AsCl3 with H2L (where L = a rigid dithiolate) results in the self-assembly of As2L2Cl2 supramolecular macrocycles. For ligands 4,4'-bis(mercaptomethyl)biphenyl (H2), 4,4'-bis(mercaptomethyl)-trans-stilbene (H2), and 1,4-dimethoxy-2,5-bis(mercaptomethyl)benzene (H2), the macrocyclic cavities of the resulting assemblies are large enough to host aromatic solvent molecules, as revealed by single crystal X-ray structures of the inclusion complexes. As2L2Cl(2) macrocycles form in solution as a mixture of diastereomers, but the diastereomers can be selectively crystallized and separated. Crystallization of syn- or anti-As(2)3(2)Cl2 can be controlled using host-guest interactions by the prudent choice of crystallization solvents. anti-As(2)3(2)Cl2 crystallizes exclusively from chloroform and benzene, while a [(syn-As(2)(2)Cl(2))(2).p-xylene] dimer crystallizes from p-xylene and a mixture of [(syn-As(2)3(2)Cl(2))(anti-As(2)3(2)Cl2) x toluene] and [(syn-As(2)3(2)Cl2)2 x toluene] dimers crystallize from toluene.
三氯化砷与H₂L（其中L = 一种刚性二硫醇盐）反应会导致As₂L₂Cl₂超分子大环的自组装。对于配体4,4'-双（巯基甲基）联苯（H₂）、4,4'-双（巯基甲基）-反式芪（H₂）和1,4-二甲氧基-2,5-双（巯基甲基）苯（H₂），所得组装体的大环空腔足够大，可以容纳芳香族溶剂分子，这一点通过包合物的单晶X射线结构得以揭示。As₂L₂Cl₂大环在溶液中以非对映异构体混合物的形式形成，但这些非对映异构体可以被选择性地结晶和分离。通过谨慎选择结晶溶剂利用主客体相互作用，可以控制顺式或反式As₂L₂Cl₂的结晶。反式As₂L₂Cl₂仅从氯仿和苯中结晶出来，而[(顺式As₂L₂Cl₂)₂·对二甲苯]二聚体从对二甲苯中结晶出来，[(顺式As₂L₂Cl₂)(反式As₂L₂Cl₂)·甲苯]和[(顺式As₂L₂Cl₂)₂·甲苯]二聚体从甲苯中结晶出来。
