Homoconjugation and Intramolecular Charge Transfer in Extended Aromatic Triptycenes with Different π-Planes

被引:26
作者
Baumgaertner, Kevin [1 ]
Hoffmann, Marvin [2 ]
Rominger, Frank [1 ]
Elbert, Sven M. [1 ]
Dreuw, Andreas [2 ]
Mastalerz, Michael [1 ]
机构
[1] Heidelberg Univ, Organ Chem Inst, D-69120 Heidelberg, Germany
[2] Heidelberg Univ, Interdisziplinares Zentrum Wissensch Rechnen, D-69120 Heidelberg, Germany
关键词
PARAMAGNETIC RESONANCE; TRANSFER TRANSITION; MIXED-VALENCE; SPECTRA; DERIVATIVES; QUINONE;
D O I
10.1021/acs.joc.0c02100
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Homoconjugation and intramolecular "through-space" charge transfers are molecular phenomena that have been studied since the 1960s. A detailed understanding and control of these effects would provide a tool to tune the optoelectronic properties of organic molecules in respect of the necessities for applications such as for organic electronics. Triptycene is a perfect candidate to investigate homoconjugation effects due to its three-dimensional alignment of three aromatic phenylene units, separated by two methine bridges. Here, a series of pi-extended triptycenes with up to three different permuted electron-accepting units and an electron-rich veratrole unit are studied in detail by UV/vis spectroscopy and cyclovoltammetry in combination with DFT calculations to get a deeper understanding of homoconjugation and charge-transfer processes of triptycenes. Furthermore, the gained knowledge can be exploited to construct triptycene-based electron acceptors with fine-tuned adjustment of electronic properties, such as electron affinities, by thorough choice of the aromatic blades that interact through homoconjugation.
引用
收藏
页码:15256 / 15272
页数:17
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