Castilla Ana M, Miller Mark A, Nitschke Jonathan R, Smulders Maarten M J
Department of Chemistry University of Cambridge Cambridge CB2 1EW UK.
Department of Chemistry Durham University South Road Durham DH1 3LE UK.
Angew Chem Weinheim Bergstr Ger. 2016 Aug 26;128(36):10774-10778. doi: 10.1002/ange.201602968. Epub 2016 Jun 2.
The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal-organic assemblies is reported. The factors affecting the stereochemical communication within and between the metal stereocenters of the assemblies were experimentally studied by optical spectroscopy and analyzed in terms of a free energy penalty per "incorrect" amine enantiomer incorporated, and a free energy of coupling between stereocenters. These intra- and inter-vertex coupling constants are used to track the degree of stereochemical communication across a range of metal-organic assemblies (employing different ligands, peripheral amines, and metals); temperature-dependent equilibria between diastereomeric cages are also quantified. The model thus provides a unified understanding of the factors that shape the chirotopic void spaces enclosed by metal-organic container molecules.
本文报道了一种统计力学模型的推导及其在量化金属有机组装体中立体化学通讯方面的应用。通过光谱学实验研究了影响组装体金属立体中心内部和之间立体化学通讯的因素，并根据每个掺入的“错误”胺对映体的自由能罚值以及立体中心之间的耦合自由能进行了分析。这些顶点内和顶点间的耦合常数用于跟踪一系列金属有机组装体（使用不同的配体、外围胺和金属）中的立体化学通讯程度；非对映异构笼之间的温度依赖性平衡也进行了量化。该模型因此提供了对塑造金属有机容器分子所包围的手性空穴空间的因素的统一理解。
