Chang Liu, Lunxiang Yin, Xu Wang, Yaru Liu, Yanqin Li
{"title":"双桥 N-B←N 双吡啶基翼形小分子染料:π 桥对光电性能的调控","authors":"Chang Liu, Lunxiang Yin, Xu Wang, Yaru Liu, Yanqin Li","doi":"10.1016/j.dyepig.2024.112319","DOIUrl":null,"url":null,"abstract":"<div><p>The double-bridged N–B<strong>←</strong>N bipyridine unit (BNBP) with boron-nitrogen covalent bond and coordination bond can reduce the electronic energy level of the π-conjugated system, resulting in a reduction of band gap and a red shift in the absorption spectrum. Embedding the BNBP building block into organic optoelectronic materials provides a novel possibility in molecule design. In this paper, under the guidance of density functional theory (DFT) calculations, a series of 3D “airfoil-shaped” small molecule donors (SMDs) have been designed and successfully synthesized through Sonogashira, Suzuki and Stille coupling reactions. BNBP is adopted as the central electron-withdrawing unit and strong electron-rich triphenylamine (TPA) as the terminal group. The novel “airfoil-shaped” structure plays a supporting role in reducing the carrier recombination in the active layer. It reveals that molecular design engineering can achieve the expected results by the following steps: Firstly, the introduction of electron-rich alkoxy groups into the end of TPA through side chain engineering helps to improve the solubility and film-forming properties of the materials. Then, the π-bridge regulation not only extends the conjugate structure, but also plays a crucial role in the regulation of photovoltaic properties. It is worth noting that the compound <strong>BNBP(3TTPA)</strong><sub><strong>2</strong></sub> was synthesized by introducing thiophene oligomer into BNBP-based SMDs for the first time. Finally, the compound <strong>BNBP(EDPPTPA)</strong><sub><strong>2</strong></sub> was constructed by combining BNBP with DPP dye unit. Its narrow band gap is only 1.36 eV, which is one of the narrowest band gaps in small molecular organic-boron materials. In particular, compared with the starting compound <strong>BNBP(ETPA)</strong><sub><strong>2</strong></sub>, the synergistic effects of DPP and BNBP broaden the edge absorption wavelength to 814 nm, resulting in a red shift of 170 nm. The power conversion efficiency (PCE) of 4.48 % is obtained in <strong>BNBP(EDPPTPA)</strong><sub><strong>2</strong></sub>-based bulk heterojunction (BHJ) organic solar cells (OSCs), which is more than twice that of reference compound <strong>BNBP(ETPA)</strong><sub><strong>2</strong></sub>. This work provides important references for the future development of 3D BNBP-based organic-boron SMDs and the structural regulation of materials through molecular engineering.</p></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":null,"pages":null},"PeriodicalIF":4.1000,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Double-bridged N–B←N bipyridyl-based airfoil-shaped small molecule dyes: π-bridge regulation on photovoltaic performance\",\"authors\":\"Chang Liu, Lunxiang Yin, Xu Wang, Yaru Liu, Yanqin Li\",\"doi\":\"10.1016/j.dyepig.2024.112319\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The double-bridged N–B<strong>←</strong>N bipyridine unit (BNBP) with boron-nitrogen covalent bond and coordination bond can reduce the electronic energy level of the π-conjugated system, resulting in a reduction of band gap and a red shift in the absorption spectrum. Embedding the BNBP building block into organic optoelectronic materials provides a novel possibility in molecule design. In this paper, under the guidance of density functional theory (DFT) calculations, a series of 3D “airfoil-shaped” small molecule donors (SMDs) have been designed and successfully synthesized through Sonogashira, Suzuki and Stille coupling reactions. BNBP is adopted as the central electron-withdrawing unit and strong electron-rich triphenylamine (TPA) as the terminal group. The novel “airfoil-shaped” structure plays a supporting role in reducing the carrier recombination in the active layer. It reveals that molecular design engineering can achieve the expected results by the following steps: Firstly, the introduction of electron-rich alkoxy groups into the end of TPA through side chain engineering helps to improve the solubility and film-forming properties of the materials. Then, the π-bridge regulation not only extends the conjugate structure, but also plays a crucial role in the regulation of photovoltaic properties. It is worth noting that the compound <strong>BNBP(3TTPA)</strong><sub><strong>2</strong></sub> was synthesized by introducing thiophene oligomer into BNBP-based SMDs for the first time. Finally, the compound <strong>BNBP(EDPPTPA)</strong><sub><strong>2</strong></sub> was constructed by combining BNBP with DPP dye unit. Its narrow band gap is only 1.36 eV, which is one of the narrowest band gaps in small molecular organic-boron materials. In particular, compared with the starting compound <strong>BNBP(ETPA)</strong><sub><strong>2</strong></sub>, the synergistic effects of DPP and BNBP broaden the edge absorption wavelength to 814 nm, resulting in a red shift of 170 nm. The power conversion efficiency (PCE) of 4.48 % is obtained in <strong>BNBP(EDPPTPA)</strong><sub><strong>2</strong></sub>-based bulk heterojunction (BHJ) organic solar cells (OSCs), which is more than twice that of reference compound <strong>BNBP(ETPA)</strong><sub><strong>2</strong></sub>. This work provides important references for the future development of 3D BNBP-based organic-boron SMDs and the structural regulation of materials through molecular engineering.</p></div>\",\"PeriodicalId\":302,\"journal\":{\"name\":\"Dyes and Pigments\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.1000,\"publicationDate\":\"2024-07-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dyes and Pigments\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S014372082400384X\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dyes and Pigments","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S014372082400384X","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Double-bridged N–B←N bipyridyl-based airfoil-shaped small molecule dyes: π-bridge regulation on photovoltaic performance
The double-bridged N–B←N bipyridine unit (BNBP) with boron-nitrogen covalent bond and coordination bond can reduce the electronic energy level of the π-conjugated system, resulting in a reduction of band gap and a red shift in the absorption spectrum. Embedding the BNBP building block into organic optoelectronic materials provides a novel possibility in molecule design. In this paper, under the guidance of density functional theory (DFT) calculations, a series of 3D “airfoil-shaped” small molecule donors (SMDs) have been designed and successfully synthesized through Sonogashira, Suzuki and Stille coupling reactions. BNBP is adopted as the central electron-withdrawing unit and strong electron-rich triphenylamine (TPA) as the terminal group. The novel “airfoil-shaped” structure plays a supporting role in reducing the carrier recombination in the active layer. It reveals that molecular design engineering can achieve the expected results by the following steps: Firstly, the introduction of electron-rich alkoxy groups into the end of TPA through side chain engineering helps to improve the solubility and film-forming properties of the materials. Then, the π-bridge regulation not only extends the conjugate structure, but also plays a crucial role in the regulation of photovoltaic properties. It is worth noting that the compound BNBP(3TTPA)2 was synthesized by introducing thiophene oligomer into BNBP-based SMDs for the first time. Finally, the compound BNBP(EDPPTPA)2 was constructed by combining BNBP with DPP dye unit. Its narrow band gap is only 1.36 eV, which is one of the narrowest band gaps in small molecular organic-boron materials. In particular, compared with the starting compound BNBP(ETPA)2, the synergistic effects of DPP and BNBP broaden the edge absorption wavelength to 814 nm, resulting in a red shift of 170 nm. The power conversion efficiency (PCE) of 4.48 % is obtained in BNBP(EDPPTPA)2-based bulk heterojunction (BHJ) organic solar cells (OSCs), which is more than twice that of reference compound BNBP(ETPA)2. This work provides important references for the future development of 3D BNBP-based organic-boron SMDs and the structural regulation of materials through molecular engineering.
期刊介绍:
Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied.
Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media.
The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.