Molecular tetrominoes: selective masking of the donor π-face to control the configuration of donor–acceptor complexes
Molecular tetrominoes: selective masking of the donor π-face to control the configuration of donor–acceptor complexes
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分子四联骨牌：选择性掩蔽供体α面以控制供体受体复合物的构型
DOI：
10.1039/d1ob02293h
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发表时间：
2022
影响因子：
3.2
通讯作者：
Gavvalapalli, Nagarjuna
中科院分区：
文献类型：
--
作者：
Sartucci, Jenna L.;Maity, Arindam;Mohanan, Manikandan;Bertke, Jeffery;Kertesz, Miklos;Gavvalapalli, Nagarjuna
了解有机半导体中的掺杂机理并产生分子设计规则来控制掺杂过程对于提高有机电子学性能至关重要。尽管控制掺杂剂沿着半导体主干的位置和取向是掺杂机制中的重要步骤，但由于这是一项具有挑战性的任务，因此在该方向上的研究很少。为了解决这个问题，本文中，我们在1，4-双（苯基亚乙炔基）苯（供体）中引入π-面掩蔽（束缚）单元以控制受体（掺杂剂）沿着三聚体的位置、供体-受体结合强度和受体电离。两个捆绑的三聚体，PCP和CPC，合成控制捆绑的重复单元在三聚体中的位置。三聚体在溶液中与2，3-二氯-5，6-二氰基-1，4-苯醌（DDQ）受体络合。DFT计算表明，DDQ驻留在非束缚重复单元上（这种构型的百分比至少为约10%）。73%）对PCP和CPC具有最高的结合能。与线性对照三聚体（PLP和LPL）和完全非束缚（PPP）三聚体相比，在束缚三聚体（PCP和CPC）的情况下掺杂剂电离的百分比更高。与PPP相比，PCP和CPC的掺杂剂电离百分比分别增加了15%和59%。
Understanding the doping mechanism in organic semiconductors and generating molecular design rules to control the doping process are crucial for improving the performance of organic electronics. Even though controlling the location and orientation of the dopant along the semiconductor backbone is an important step in the doping mechanism, studies in this direction are scarce as it is a challenging task. To address this, herein, we incorporated π-face masked (strapped) units in 1,4-bis(phenylethynylene)benzene (donor) to control the acceptor (dopant) location along the trimer, donor–acceptor binding strength, and acceptor ionization. Two strapped trimers, PCP and CPC, are synthesized with control over the location of the strapped repeat unit in the trimer. The trimers are complexed with the 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) acceptor in solution. DFT calculations show that DDQ residing on the non-strapped repeat unit (the percentage of this configuration is at least ca. 73%) has the highest binding energy for both PCP and CPC. The percentage of dopant ionization is higher in the case of strapped trimers (PCP and CPC) compared to that of linear control trimers (PLP and LPL) and the completely non-strapped (PPP) trimer. The percentage of dopant ionization increased by 15 and 59% in the case of PCP and CPC respectively compared to that of PPP.