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
[11]   N-Heteroacenes [J].
Bunz, Uwe H. F. .
CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (28) :6780-6789
[12]   Triptycene-Derived Macrocyclic Arenes: From Calixarenes to Helicarenes [J].
Chen, Chuan-Feng ;
Han, Ying .
ACCOUNTS OF CHEMICAL RESEARCH, 2018, 51 (09) :2093-2106
[13]   Balancing volumetric and gravimetric uptake in highly porous materials for clean energy [J].
Chen, Zhijie ;
Li, Penghao ;
Anderson, Ryther ;
Wang, Xingjie ;
Zhang, Xuan ;
Robison, Lee ;
Redfern, Louis R. ;
Moribe, Shinya ;
Islamoglu, Timur ;
Gomez-Gualdron, Diego A. ;
Yildirim, Taner ;
Stoddart, J. Fraser ;
Farha, Omar K. .
SCIENCE, 2020, 368 (6488) :297-+
[14]   Reticular exploration of uranium-based metal-organic frameworks with hexacarboxylate building units [J].
Chen, Zhijie ;
Li, Penghao ;
Zhang, Xuan ;
Mian, Mohammad Rasel ;
Wang, Xingjie ;
Li, Peng ;
Liu, Zhichang ;
O'Keeffe, Michael ;
Stoddart, J. Fraser ;
Farha, Omar K. .
NANO RESEARCH, 2021, 14 (02) :376-380
[15]   Robust non-interpenetrating coordination frameworks from new shape-persistent building blocks [J].
Chong, JH ;
MacLachlan, MJ .
INORGANIC CHEMISTRY, 2006, 45 (04) :1442-1444
[16]   Iptycenes in supramolecular and materials chemistry [J].
Chong, Jonathan H. ;
MacLachlan, Mark J. .
CHEMICAL SOCIETY REVIEWS, 2009, 38 (12) :3301-3315
[17]   PARAMAGNETIC RESONANCE IN PHOSPHORESCENT AROMATIC HYDROCARBONS .3. CONFORMATIONAL ISOMERISM IN BENZENE AND TRIPTYCENE [J].
DEGROOT, MS ;
VANDERWAALS, JH .
MOLECULAR PHYSICS, 1963, 6 (06) :545-562
[18]   ELECTRON SPIN RESONANCE SPECTRA OF TRIPTYCENE RADICAL CATIONS [J].
DESSAU, RM .
JOURNAL OF CHEMICAL PHYSICS, 1971, 54 (12) :5430-&
[19]   HETEROCYCLIC TRIPTYCENES - SYNTHESIS AND ULTRAVIOLET SPECTROSCOPY [J].
DEWIT, J ;
WYNBERG, H .
TETRAHEDRON, 1973, 29 (10) :1379-1391
[20]   SYNTHESIS OF A RESOLVED TRIPTYCENE - SPECTROSCOPIC EVIDENCE FOR TRANSANNULAR INTERACTION [J].
DEWIT, J ;
WYNBERG, H .
TETRAHEDRON, 1972, 28 (17) :4617-&