Campbell Victoria E, de Hatten Xavier, Delsuc Nicolas, Kauffmann Brice, Huc Ivan, Nitschke Jonathan R
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
Chemistry. 2009 Jun 15;15(25):6138-42. doi: 10.1002/chem.200900693.
A rigid, helical macrocycle that contains two copper(I) ions has been synthesized through subcomponent self-assembly. Although it does not obey the "rule of coordinative saturation", this macrocycle could be prepared through subcomponent substitution starting from a tri(copper(I)) helicate, in a reaction in which copper(I) was ejected. The macrocycle was observed to readily participate in a sequence of transformations between helical structures mediated by the electronic effects of substituents, entropic effects, the conformational preferences of organic building blocks, and the coordinative preferences of the metal ion. The thermodynamic parameters governing the interconversion of an "open" helicate and the "closed" macrocycle were determined through van 't Hoff analysis, allowing quantification of the entropic driving force for macrocyclization.
通过亚组分自组装合成了一种含有两个铜（I）离子的刚性螺旋大环化合物。尽管它不遵循“配位饱和规则”，但这种大环化合物可以从三（铜（I））螺旋配合物开始，通过亚组分取代反应制备，在该反应中铜（I）被排出。观察到该大环化合物很容易参与由取代基的电子效应、熵效应、有机结构单元的构象偏好和金属离子的配位偏好介导的螺旋结构之间的一系列转变。通过范特霍夫分析确定了控制“开放”螺旋配合物和“封闭”大环化合物相互转化的热力学参数，从而能够对大环化的熵驱动力进行量化。
