Mejuto Carmen, Escobar Luis, Guisado-Barrios Gregorio, Ballester Pablo, Gusev Dmitry, Peris Eduardo
Institute of Advanced Materials (INAM)., Universitat Jaume I., Av. Vicente Sos Baynat s/n., Castellón., 12071, Spain.
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avgda. Països Catalans 16, 43007, Tarragona, Spain.
Chemistry. 2017 Aug 4;23(44):10644-10651. doi: 10.1002/chem.201701728. Epub 2017 Jul 13.
The deprotonation of a corannulene-based bisazolium salt allowed the preparation of a corannulene-based NHC di-Au complex. The prepared di-Au -complex was tested in the recognition of fullerene-C , demonstrating good binding affinity in toluene solution, and producing a host-guest complex with 3:1 stoichiometry, as evidenced by a combination of NMR spectroscopy and ITC titrations. The experimental results are fully supported by DFT calculations. The binding of C with the di-Au complex in toluene solution is enthalpically and entropically favoured. Remarkably, the entropic term is the dominant parameter in the binding process. The good complementarity that exists between the concave shape of the corannulene-di-gold complex and the convex surface of the fullerene, together with the presence of tBu groups and the AuCl fragment are key factors for the measured high affinity between host and guest. The obtained results indicate that fullerene may be acting as a template for the formation of a self-assembled aggregate involving up to three molecules of the di-Au complex.
基于碗烯的双唑鎓盐的去质子化反应使得制备基于碗烯的NHC双金配合物成为可能。所制备的双金配合物在对富勒烯-C的识别中进行了测试，在甲苯溶液中显示出良好的结合亲和力，并生成了化学计量比为3:1的主客体配合物，这通过核磁共振光谱和等温滴定量热法滴定得到了证实。实验结果得到了密度泛函理论计算的充分支持。在甲苯溶液中，C与双金配合物的结合在焓和熵方面都是有利的。值得注意的是，熵项是结合过程中的主导参数。碗烯 - 二金配合物的凹形与富勒烯的凸面之间存在的良好互补性，以及叔丁基基团和AuCl片段的存在，是测得的主客体之间高亲和力的关键因素。所得结果表明，富勒烯可能作为模板参与形成包含多达三个双金配合物分子的自组装聚集体。
