mPW1PW91-Calculated Structures, IR Spectra, and Frontier Orbitals of 1,2-Bridged Calix[4]aryl Picrate Complexed with Alkali Metal Ions

作者：Ham Seung Wook; Choe Jong In^*

来源：BULLETIN OF THE KOREAN CHEMICAL SOCIETY, 2015, 36(5): 1474-1486.

DOI：10.1002/bkcs.10289

• mPW1PW91
• Complex
• Conformer
• Alkali metal ion
• 1,2-Bridged calix[4]aryl picrate

The molecular structures of three conformers (cone [CONE], partial cone [PACO], and 1,2-alternate [12A]) of 1,2-bridged calix[4]aryl picrate 1 and their alkali-metal-ion complexes were optimized using a mPW1PW91/6-31G(d,p) (hybrid HF-DF) calculation method. The total electronic and relative binding energies and the gaps of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) frontier orbitals of the complexes of each conformer with sodium and potassium ions were analyzed. The HOMOs are mainly concentrated in the phenyl rings in calix skeleton as bonding orbitals, while the LUMOs are located in the picrate moieties as anti-bonding orbitals. The monotopic binding efficiency of the 1(CONE)Na+(exo) complex (-98.0kcal/mol) was the strongest among the six kinds of the Na+ complexes and much better than that of the 1(12A)K+(exo) complex (-77.8kcal/mol). The IR spectra of the conformers of 1 and their complexes with the alkali metal ions were calculated by mPW1PW91 and analyzed.

• 出版日期2015-5