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Substituent-dependent absorption and fluorescence properties of perylene bisimide radical anions and dianions
Materials Horizons ( IF 12.2 ) Pub Date : 2021-08-05 , DOI: 10.1039/d1mh01019k Rebecca Renner 1 , Matthias Stolte 1, 2 , Julia Heitmüller 3 , Tobias Brixner 2, 3 , Christoph Lambert 1, 2 , Frank Würthner 1, 2
Materials Horizons ( IF 12.2 ) Pub Date : 2021-08-05 , DOI: 10.1039/d1mh01019k Rebecca Renner 1 , Matthias Stolte 1, 2 , Julia Heitmüller 3 , Tobias Brixner 2, 3 , Christoph Lambert 1, 2 , Frank Würthner 1, 2
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Perylene-3,4:9,10-bis(dicarboximides) (PBIs) rank among the most important functional dyes and organic semiconductors, but only recently have their radical anions and dianions attracted interest for a variety of applications. Here, we systematically elucidate the functional properties (redox, absorption, and emission) of five PBI anions and dianions bearing different bay-substituents attached to the chromophore core. Cyclic voltammetry measurements reveal the influence of the substituents ranging from electron-withdrawing cyano to electron-donating phenoxy groups on the oxidation and reduction potentials that relate to the HOMO and LUMO levels ranging from −7.07 eV to −6.05 eV and −5.01 eV to −4.05 eV, respectively. Spectroelectrochemical studies reveal a significant number of intense absorption bands in the NIR-spectral range (750–1400 nm) for the radical anions, whereas the dianionic species are characterized by similar spectra to those for the neutral dyes, however being bathochromically shifted and with increased molar extinction coefficients of approximately 100 000 M−1 cm−1. The increase of the transition dipole moment is up to 56% and accompanied by an almost cyanine-like red-shifted (by 300 nm) absorption spectrum for the most electron-poor tetracyanotetrachloro PBI. Whilst the outstanding fluorescence properties of the neutral PBIs are lost for the radical anions, an appreciable near-infrared (NIR) fluorescence with a quantum yield of up to 18% is revealed for the dianions by utilizing a custom-built flow-cell spectroelectrochemistry setup. Time-dependent density functional theory calculations help to assign the absorption bands to the respective electronic transitions.
中文翻译：
苝双酰亚胺自由基阴离子和二价阴离子的取代基吸收和荧光特性
苝-3,4:9,10-双（二甲酰亚胺）（PBI）是最重要的功能染料和有机半导体之一，但直到最近，它们的自由基阴离子和二价阴离子才引起了各种应用的兴趣。在这里，我们系统地阐明了五种 PBI 阴离子和二价阴离子的功能特性（氧化还原、吸收和发射），这些阴离子和二价阴离子带有附着在发色团核心上的不同海湾取代基。循环伏安法测量揭示了从吸电子氰基到供电子苯氧基的取代基对与 HOMO 和 LUMO 能级相关的氧化和还原电位的影响，范围从 -7.07 eV 到 -6.05 eV 和 -5.01 eV 到 -分别为 4.05 eV。-1厘米-1。对于最缺电子的四氰基四氯 PBI，跃迁偶极矩的增加高达 56%，并伴随着几乎类似花青的红移（300 nm）吸收光谱。虽然自由基阴离子失去了中性 PBI 的出色荧光特性，但通过使用定制的流动池光谱电化学装置，双阴离子显示了可观的近红外 (NIR) 荧光，其量子产率高达 18% . 瞬态密度泛函理论计算有助于将吸收带分配给相应的电子跃迁。
更新日期：2021-08-05
中文翻译：
苝双酰亚胺自由基阴离子和二价阴离子的取代基吸收和荧光特性
苝-3,4:9,10-双（二甲酰亚胺）（PBI）是最重要的功能染料和有机半导体之一，但直到最近，它们的自由基阴离子和二价阴离子才引起了各种应用的兴趣。在这里，我们系统地阐明了五种 PBI 阴离子和二价阴离子的功能特性（氧化还原、吸收和发射），这些阴离子和二价阴离子带有附着在发色团核心上的不同海湾取代基。循环伏安法测量揭示了从吸电子氰基到供电子苯氧基的取代基对与 HOMO 和 LUMO 能级相关的氧化和还原电位的影响，范围从 -7.07 eV 到 -6.05 eV 和 -5.01 eV 到 -分别为 4.05 eV。-1厘米-1。对于最缺电子的四氰基四氯 PBI，跃迁偶极矩的增加高达 56%，并伴随着几乎类似花青的红移（300 nm）吸收光谱。虽然自由基阴离子失去了中性 PBI 的出色荧光特性，但通过使用定制的流动池光谱电化学装置，双阴离子显示了可观的近红外 (NIR) 荧光，其量子产率高达 18% . 瞬态密度泛函理论计算有助于将吸收带分配给相应的电子跃迁。
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