Tuning the Quinoid versus Biradicaloid Character of Thiophene-Based Heteroquaterphenoquinones by Means of Functional Groups

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• 作者：Eleonora V. Canesi ; Daniele Fazzi ; Letizia Colella ; Chiara Bertarelli ; Chiara Castiglioni
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：November 21, 2012
• 年：2012
• 卷：134
• 期：46
• 页码：19070-19083
• 全文大小：672K
• 年卷期：v.134,no.46(November 21, 2012)
• ISSN：1520-5126

文摘

A series of quinoidal bithiophenes (QBTs) with controlled variations in steric hindrance and electron activity of the substituents has been synthesized. Evidence of their quinoidal versus biradicaloid ground-state electronic character has been experimentally detected and coherently identified as fingerprints by spectroscopic methods such as NMR, UV鈥搗is, multiwavelength Raman. From this analysis, alkoxy groups have been shown to strongly affect the electronic structure and the ground-state energy and stability of QBTs. Quantum-chemical calculations correctly predict the experimental spectroscopic response, even while changing the alkyl on phenone from a tertiary carbon atom to secondary to primary toward an unsubstituted phenone, further confirming the validity of the approach proposed. A control of the electronic structure accompanied by negligible variations of the optical gap of the molecules has thus been demonstrated, extending the potential use of quinoidal species in fields ranging from photon harvesting to magnetic applications.