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
相关论文
共 70 条
[1]   Enantioselective Synthesis of Distorted π-Extended Chiral Triptycenes Consisting of Three Distinct Aromatic Rings by Rhodium-Catalyzed [2+2+2] Cycloaddition [J].
Aida, Yukimasa ;
Shibata, Yu ;
Tanaka, Ken .
CHEMISTRY-A EUROPEAN JOURNAL, 2020, 26 (14) :3004-3009
[2]   DISPLACEMENT REACTIONS AT BRIDGEHEADS OF BRIDGED POLYCARBOCYCLIC SYSTEMS [J].
APPLEQUIST, DE ;
ROBERTS, JD .
CHEMICAL REVIEWS, 1954, 54 (06) :1065-1089
[3]   Triptycene (9,10-o-benzenoanthracene [J].
Bartlett, PD ;
Ryan, MJ ;
Cohen, SG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1942, 64 :2649-2653
[4]   BICYCLIC STRUCTURES PROBHIBITING THE WALDEN INVERSION - FURTHER STUDIES ON TRIPTYCENE AND ITS DERIVATIVES, INCLUDING 1-BROMOTRIPTYCENE [J].
BARTLETT, PD ;
LEWIS, ES .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1950, 72 (02) :1005-1009
[5]   TRIPTYCENE 1-CARBOXYLIC ACID AND RELATED COMPOUNDS - THE DECOMPOSITION OF DITRIPTOYL PEROXIDE [J].
BARTLETT, PD ;
GREENE, FD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1954, 76 (04) :1088-1096
[6]   A Conformationally Stable Contorted Hexabenzoovalene [J].
Baumgaertner, Kevin ;
Chincha, Ana Lucia Meza ;
Dreuw, Andreas ;
Rominger, Frank ;
Mastalerz, Michael .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (50) :15594-15598
[7]   An Oxidative Macrobicyclic Ring Opening of a Triptycene to a Highly Functionalized Fluorene Derivative [J].
Baumgaertner, Kevin ;
Rominger, Frank ;
Mastalerz, Michael .
JOURNAL OF ORGANIC CHEMISTRY, 2015, 80 (17) :8881-8886
[8]  
Baumgartner K., 2018, THESIS RUPRECHT KARL
[9]   ABSORPTION SPECTRA OF KETONES .6. INTRAMOLECULAR CHARGE-TRANSFER SPECTRA, AND FURTHER EXAMPLES OF INTENSIFIED N-]PI] TRANSITIONS [J].
BIRNBAUM, H ;
COOKSON, RC ;
LEWIN, N .
JOURNAL OF THE CHEMICAL SOCIETY, 1961, (MAR) :1224-&
[10]   The Larger Linear N-Heteroacenes [J].
Bunz, Uwe H. F. .
ACCOUNTS OF CHEMICAL RESEARCH, 2015, 48 (06) :1676-1686