Lande Dipali N, Rao Soniya S, Gejji Shridhar P
Department of Chemistry, Savitribai Phule Pune University, Pune, India.
Chemphyschem. 2016 Jul 18;17(14):2197-209. doi: 10.1002/cphc.201600186. Epub 2016 Apr 18.
Binding of novel biphene[n]arene hosts to antiaromatic 7,7,8,8-tetracyanoquinodimethane (TCNQ) are investigated by DFT. Biphene[4]arene favors the inclusion complex through noncovalent interactions, such as hydrogen bonding, π-π stacking, C-H⋅⋅⋅π, and C-H⋅⋅⋅H-C dihydrogen bonding. Donor-acceptor complexation renders aromatic character to the guest through charge transfer. The formation of TCNQ anionic radicals through supramolecular π stacking significantly influences its chemical and photophysical behavior. Electron density reorganization consequent to encapsulation of TCNQ reflects in the shift of characteristic vibrations in the IR spectra. The accompanying aromaticities arising from the induced ring currents are analyzed by employing nucleus-independent chemical shifts based profiles.
通过密度泛函理论（DFT）研究了新型联苯[n]芳烃主体与反芳香性的7,7,8,8-四氰基对苯二醌二甲烷（TCNQ）的结合。联苯[4]芳烃通过氢键、π-π堆积、C-H⋅⋅⋅π和C-H⋅⋅⋅H-C双氢键等非共价相互作用形成包合配合物。供体-受体络合通过电荷转移赋予客体芳香性。通过超分子π堆积形成TCNQ阴离子自由基显著影响其化学和光物理行为。TCNQ被包封后电子密度的重新排列反映在红外光谱中特征振动的位移上。通过基于核独立化学位移的图谱分析了由诱导环电流产生的伴随芳香性。
