对硝基杯[8]芳烃的合成及其与奥克托今的配合

Synthesis of p-Nitrocalix[8] arene and p-Nitrocalix[8] arene-HMX Supramolecular Complex

以对叔丁基苯酚与多聚甲醛为原料合成了对硝基杯[8]芳烃。利用紫外光谱研究了对硝基杯[8]芳烃与奥克托今(HMX)在氯仿中的配合性能。用量子化学半经验AM1和ab initio HF/3-21G方法,分别得到主、客体及其超分子体系几何全优化结构。结果表明,主客体分子形成了1∶1的配合物,标准状况下对硝基杯[8]芳烃与HMX形成超分子体系后较单体能量之和减少60.76 kJ/mol,主客体间可形成氢键。对硝基杯[8]芳烃与HMX超分子体系的稳定常数Kw从288 K的1.138×1012降至408 K时的1.121×105。

p-Nitro-calix[ 8 ] arene was synthesized with p-t-butyl-calix[ 8 ] arene and paraform as starting materials. The complex characteristics of p-nitro-calix [ 8 ] arene and HMX in CHCl3 was studied by UV-visible spectroscopy. The optimized monomers and conformer of p-nitro-calix[ 8 ] arene with HMX have been obtained with quantum chemistry half-empirical AMland ab initio HF/3-21G methods, respectively. The result reveals that the relative quantity ratio is 1： 1. The intermolecular interaction energy of the supramolecular complex is 60. 76 kJ/mol, indicating that hydrogen bond is formed between p-nitro-calix [ 8 ] arene and HMX. In the mean time, the changes of thermodynamic properties from the monomers to supermolecules with the temperature ranged from 288 to 408 K were obtained via the statistical thermodynamics by AM1 method. The stability equilibrium constant Kw of the supramolecular complex is decreased from 1. 138 × 10^12 at 288 K to 1. 121 × 10^5 at 408 K.