Impact of Ground- and Excited-State Aromaticity on Cyclopentadiene and Silole Excitation Energies and Excited-State Polarities

doi:10.1002/chem.201402577

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	Impact of Ground- and Excited-State Aromaticity on Cyclopentadiene and Silole Excitation Energies and Excited-State Polarities
	Jorner, Kjell 1; Emanuelsson, Rikard 1; Dahlstrand, Christian 1; Tong, Hui 2; Denisova, Aleksandra V.1; Ottosson, Henrik 1
刊名	CHEMISTRY-A EUROPEAN JOURNAL
	2014-07-21
卷号	20 期号:30 页码:9295-9303
关键词	Aromaticity Conjugation Density Functional Calculations Electronic Structure Organic Electronics
ISSN号	0947-6539
DOI	10.1002/chem.201402577
英文摘要	A new qualitative model for estimating the properties of substituted cyclopentadienes and siloles in their lowest pi pi* excited states is introduced and confirmed through quantum chemical calculations, and then applied to explain earlier reported experimental excitation energies. According to our model, which is based on excited-state aromaticity and antiaromaticity, siloles and cyclopentadienes are cross-hyperconjugated "aromatic chameleons" that adapt their electronic structures to conform to the various aromaticity rules in different electronic states (Huckel's rule in the pi(2) electronic ground state (S-0) and Baird's rule in the lowest pi pi* excited singlet and triplet states (S-1 and T-1)). By using pen-and-paper arguments, one can explain polarity changes upon excitation of substituted cyclopentadienes and siloles, and one can tune their lowest excitation energies by combined considerations of ground-and excited-state aromaticity/antiaromaticity effects. Finally, the "aromatic chameleon" model can be extended to other monocyclic compound classes of potential use in organic electronics, thereby providing a unified view of the S-0, T-1, and S-1 states of a range of different cyclic cross-pi-conjugated and cross-hyperconjugated compound classes.
语种	英语
出版者	WILEY-V C H VERLAG GMBH
WOS记录号	WOS:000339568800022
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/51591]
专题	中国科学院化学研究所
通讯作者	Ottosson, Henrik
作者单位	1.Uppsala Univ, Dept Chem BMC, S-75123 Uppsala, Sweden 2.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China
推荐引用方式 GB/T 7714	Jorner, Kjell,Emanuelsson, Rikard,Dahlstrand, Christian,et al. Impact of Ground- and Excited-State Aromaticity on Cyclopentadiene and Silole Excitation Energies and Excited-State Polarities[J]. CHEMISTRY-A EUROPEAN JOURNAL,2014,20(30):9295-9303.
APA	Jorner, Kjell,Emanuelsson, Rikard,Dahlstrand, Christian,Tong, Hui,Denisova, Aleksandra V.,&Ottosson, Henrik.(2014).Impact of Ground- and Excited-State Aromaticity on Cyclopentadiene and Silole Excitation Energies and Excited-State Polarities.CHEMISTRY-A EUROPEAN JOURNAL,20(30),9295-9303.
MLA	Jorner, Kjell,et al."Impact of Ground- and Excited-State Aromaticity on Cyclopentadiene and Silole Excitation Energies and Excited-State Polarities".CHEMISTRY-A EUROPEAN JOURNAL 20.30(2014):9295-9303.