Furer V L, Borisoglebskaya E I, Zverev V V, Kovalenko V I
Kazan State Architect and Civil Engineering Academy, Department of Physics, 1 Zelenaya, 420043 Kazan, Russia.
Spectrochim Acta A Mol Biomol Spectrosc. 2005 Nov;62(1-3):483-93. doi: 10.1016/j.saa.2005.02.001.
IR and far IR spectra of p-tert-butylcalix[4]arene were recorded at various temperatures between 16 and 180 degrees C and spectra of solutions and crystalline solids were obtained. Ab initio density functional calculations gave vibrational frequencies and infrared intensities for four conformers: cone, partial cone, 1,2- and 1,3-alternate. Complete assignments were made for experimental IR spectra of the cone conformer. The bands characteristic for each conformation were defined. It was revealed that O--H stretching low-frequency shift Deltanu in the cone conformation exceeds Deltanu shifts for other conformers. The effect was stipulated by a cooperative interaction of cyclic hydrogen bonds. The obtained spectra-structure correlation can be used for characteristic of calixarenes conformation.
对叔丁基杯[4]芳烃的红外光谱和远红外光谱在16至180摄氏度的不同温度下进行了记录，并获得了溶液和结晶固体的光谱。从头算密度泛函计算给出了四种构象（锥式、部分锥式、1,2-交替式和1,3-交替式）的振动频率和红外强度。对锥式构象的实验红外光谱进行了完全归属。定义了每种构象的特征谱带。结果表明，锥式构象中O-H伸缩低频位移Δν超过其他构象的Δν位移。这种效应是由环状氢键的协同相互作用规定的。所获得的光谱-结构相关性可用于杯芳烃构象的表征。
