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Volumn 63, Issue 12, 2010, Pages 1627-1633

Air-stable curved π-radical based on corannulene: Dynamic electronic-spin structure induced by temperature-dependent conformational changes

Author keywords

[No Author keywords available]

Indexed keywords

AIR-STABLE; CONFORMATIONAL CHANGE; CONJUGATED SYSTEMS; CORANNULENE; DELOCALIZATIONS; DENSITY FUNCTIONAL THEORY CALCULATIONS; ELECTRON NUCLEAR DOUBLE RESONANCE; ELECTRON SPIN RESONANCE; HIGH STABILITY; LIQUID PHASE; NEUTRAL RADICAL; NITROXIDES; SPIN STRUCTURES; TEMPERATURE DEPENDENT; TRIPLE RESONANCE;

EID: 78650153143     PISSN: 00049425     EISSN: None     Source Type: Journal    
DOI: 10.1071/CH10280     Document Type: Conference Paper
Times cited : (13)

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    • Our previous theoretical study (ref. 12c) reports that the radicalsubstituted corannulene derivatives have at least two metastable geometries with respect to the rotational motion of the radical moiety. On the basis of this finding, we have carefully determined the most stable geometry of 4.
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    • note
    • The calculated (UB3LYP/6-31G (d) level) spin densities on the carbon or nitrogen atom of the verdazyl, iminonitroxide, phenoxyl, and tert-butylnitroxide moieties attached to the corannulene skeleton are -0.160, -0.128, +0.349, and +0.374, respectively. These calculated results also suggest that the highest degree of extensive spindelocalized nature of 4 in comparison with 1-3 is attributable to the direct attachment of the spin centre of the tert-butylnitroxide moiety to the corannulene skeleton.
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    • N at θ = 70° seems somewhat abnormal. However, the origin is not clear at this stage.
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    • -1), respectively.
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    • 3 CN solution. This result demonstrates the occurrence of a significant π-conjugation between the radical and corannulene moieties of 4 as well as 1-3 (see also ref. 12a, b, d).
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    • -1) between the two geometries[19] in detail because the present DFT calculations do not take into account intermolecular interactions such as aggregation behaviour or solvent effects that occur under actual experimental conditions.
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    • We are also interested in 3D dynamic molecular and electronic-spin structures relevant to bowl-to-bowl inversion phenomenon of openshell systems of corannulene in a solution state, and we have already reported the calculated inversion barriers of some open-shell systems (see ref. 12e, g). In contrast to the closed-shell systems documented so far, such dynamic structures of the open-shell systems have not been experimentally investigated. The neutral radical 4 possessing the large amount of spin density on the corannulene skeleton gives a testing ground for studying the inversion behaviour. The experimental observation by pulsed-ESR technique is underway in our group. For experimental studies on the bowl-to-bowl inversion phenomenon of the closed-shell systems, see: (a) L. T. Scott, M. M. Hashemi, M. S. Bratcher, J. Am. Chem. Soc. 1992, 114, 1920. doi:10.1021/JA00031A079
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  • 55


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.