Time-dependent density functional theory study of the excited-state dihydrogen bonding: clusters of 2-pyridone with diethylmethylsilane and triethylgermanium.
Density functional theory (DFT) was carried out to identify the existence of intermolecular dihydrogen bonds of the 2-pyridone (2PY)-diethylmethylsilane (DEMS) and 2PY-triethylgermanium (TEGH) clusters in the ground state. The H···H distances of both clusters are shorter than the sum of their van der Waals radii. Thus, intermolecular dihydrogen bonds N-H•••H-Si and N-H•••H-Ge exist in the 2PY-DEMS and 2PY-TEGH clusters, respectively. Based on the ground-state conformations, intermolecular dihydrogen bonds N-H•••H-Si and N-H•••H-Ge in the electronically excited state of the 2PY-DEMS and 2PY-TEGH clusters were also investigated using time-dependent density functional theory (TDDFT). Electronic transition of the 2PY-DEMS cluster resembles that of the 2PY-TEGH cluster. Their S(1) state is a locally excited (LE) state centered on 2PY moiety. The H•••H distances of the 2PY-DEMS and 2PY-TEGH clusters both stretch in the S(1) state compared to those in the ground state. Upon electronic excitation, intermolecular dihydrogen bonding N-H•••H-Si and N-H•••H-Ge can weaken with decreasing dihydrogen bonding energies.
State Key Laboratory of Fine Chemicals, School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024, China.
Ning-Ning
NN
Wei
Ce
C
Hao
Jiao-Jie
JJ
Tan
Guangyan
G
Zhao
Ruizhou
R
Li
Zhilong
Z
Xiu
Jieshan
J
Qiu
D003198:Computer Simulation; D004581:Electronics; D005857:Germanium / Q000737:chemistry*; D006860:Hydrogen Bonding; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011728:Pyridones / Q000737:chemistry*
D009942:Organometallic Compounds; D011728:Pyridones; D005857:Germanium; C017679:2-hydroxypyridine