Yu Gilbert, Suzaki Yuji, Osakada Kohtaro
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagastuta, Midori-ku, Yokohama, 226-8503, Japan.
Chemistry Department, School of Science and Engineering, Ateneo de Manila University, Quezon City, Manila, 1108, Philippines.
Chem Asian J. 2017 Feb 1;12(3):372-377. doi: 10.1002/asia.201601554. Epub 2017 Jan 18.
Dibenzo[24]crown-8 (DB24C8) forms rotaxanes with a linear molecule having a dialkylammonium group and a triazole group as well as with the acetylation product of a cationic axle molecule. The former cationic rotaxane is stabilized by multiple intermolecular hydrogen bonds between the NH and oxyethylene groups. The neutral rotaxane contains the macrocycle in the vicinity of the terminal aryl group. The co-conformation of both the cationic and neutral rotaxanes can be fixed by coordination of the triazole group of the axle molecule to PtCl (dmso) . A H NMR spectroscopic study on the thermodynamics of the Pt coordination revealed a larger association constant for the rotaxanes than for the corresponding axle molecules and a larger value for the neutral rotaxane than for the cationic rotaxane.
二苯并[24]冠-8（DB24C8）与具有二烷基铵基团和三唑基团的线性分子以及阳离子轴分子的乙酰化产物形成轮烷。前一种阳离子轮烷通过NH与氧化乙烯基团之间的多个分子间氢键得以稳定。中性轮烷在末端芳基附近含有大环。阳离子和中性轮烷的共构象可通过轴分子的三唑基团与PtCl（dmso）配位来固定。一项关于Pt配位热力学的1H NMR光谱研究表明，轮烷的缔合常数比相应轴分子的缔合常数大，且中性轮烷的值比阳离子轮烷的值大。
