ICCAS OpenIR
Conformations of stilbene-like species and new method of energy partition
Yu, ZH; Li, LT; Fu, W; Li, LP
1998-03-12
Source PublicationJOURNAL OF PHYSICAL CHEMISTRY A
ISSN1089-5639
Volume102Issue:11Pages:2016-2028
AbstractTo understand the nature of pi-electron delocalization, while questioning the abnormally large twist angle of N-benzylideneaniline, we prepared four stilbene-like species, (4-X-Ph)-CH=N-Ar (Ar = 2-pyridyl, X= -Cl, -NO2, -N(Me)(2): Ar = 2-pyrimidyl, X = -NO2), and four ketenimine derivatives, (4-X-Ph)(2)C=C=N-(Ph-Y-4) (Y=-H, X=-H; Y=-NO2, X=-H; Y=-NO2, X=-OMe; Y=-N(Me)(2), X=-H), and determined their crystal structures using X-ray difl%action. Our new procedure for constructing a complete fragment molecular orbital (FMO) basis set is described in detail. Based on our procedure, the Morokuma's energy partitioning provides, in the framework of ab initio SCF-MO computation at the STO-3G level, the various pi and sigma energies associated with the inter-and intrafragment interactions. The pi-electron delocalization in the DPI state of stilbene-like species is found to be destabilization. The DPI state is most destabilized at the coplanar geometry, and its electronic energy is the highest of four hypothetical electronic states. The characteristics of the quantum mechanical resonance energy (QMRE), including its role with regard to chemical reactivities toward electrophile attack, depend upon the response of the a framework to the pi-electron delocalization. In the case of stilbene-like species, the QMRE is destabilizing. Conversely, the QMRE of benzene is stabilizing. However, it is the cr framework of benzene, rather than the sr system itself, which is strongly stabilized by the QMRE, revealing that benzene is a aromatic. The driving forces for the out-of-plane twist of stilbene-like species arise from the QMRE and the sigma orbital interaction. The electron-withdrawing (-I) groups and the ring-nitrogen atoms seem to have an obvious influence upon the twist angle.
Indexed BySCI
Language英语
WOS IDWOS:000072622400019
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:28[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/74590
Collection中国科学院化学研究所
Corresponding AuthorYu, ZH
AffiliationChinese Acad Sci, Inst Chem, Beijing 100080, Peoples R China
Recommended Citation
GB/T 7714
Yu, ZH,Li, LT,Fu, W,et al. Conformations of stilbene-like species and new method of energy partition[J]. JOURNAL OF PHYSICAL CHEMISTRY A,1998,102(11):2016-2028.
APA Yu, ZH,Li, LT,Fu, W,&Li, LP.(1998).Conformations of stilbene-like species and new method of energy partition.JOURNAL OF PHYSICAL CHEMISTRY A,102(11),2016-2028.
MLA Yu, ZH,et al."Conformations of stilbene-like species and new method of energy partition".JOURNAL OF PHYSICAL CHEMISTRY A 102.11(1998):2016-2028.
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