{"title":"1,1'-Binaphthalene-Functionalized 1,10-Phenanthroline 的手性铜(I)配合物的环极化电致发光","authors":"Zhi-Ping Kang, Lin-Xi Shi, Yi-Xin Wei, Jin-Yun Wang, Xu-Yang Ding, Zhong-Ning Chen","doi":"10.1021/acs.inorgchem.5c00810","DOIUrl":null,"url":null,"abstract":"This study is dedicated to the design and synthesis of novel yellow-emitting Cu(I) complex enantiomers, <i><b>R</b></i><b>/</b><i><b>S</b></i><b>-Phen-Cu-POP</b>, where the Cu(I) center is chelated by chiral 1,1’-binaphthalene-functionalized 1,10-phenanthroline (Phen) and bis(2-diphenylphosphinophenyl)ether (POP). Photophysical characterization revealed that the quantum yield (<i>Φ</i><sub>em</sub>) of <i><b>R</b></i><b>/</b><i><b>S</b></i><b>-Phen-Cu-POP</b> in CH<sub>2</sub>Cl<sub>2</sub> solutions was only 1.4–1.6%, but it significantly increased to 73.0% (<i><b>R</b></i>) and 76.1% (<i><b>S</b></i>) in PMMA doping films. Circularly polarized luminescence (CPL) studies demonstrated solid-state photoluminescence asymmetry factors (<i>g</i><sub>PL</sub>) of <i><b>R</b></i><b>/</b><i><b>S</b></i><b>-Phen-Cu-POP</b> were +8.5 × 10<sup>–3</sup> and −8.6 × 10<sup>–3</sup>. Temperature-dependent emission spectra and lifetime studies identified a small singlet–triplet energy gap (Δ<i>E</i><sub>ST</sub> = 0.073 eV), which facilitates reverse intersystem crossing (RISC) from the triplet (T<sub>1</sub>) to the singlet (S<sub>1</sub>) state, thus leading to the transformation of phosphorescence at low temperature to thermally activated delayed fluorescence (TADF) at ambient temperature. Solution-processed organic light-emitting diodes (OLEDs) achieved a maximum luminance of 1270 or 1379 cd/m<sup>2</sup>, a current efficiency of 31.8 or 30.3 cd/A, a power efficiency of 14.8 or 14.4 lm/W, and an external quantum efficiency (EQE) of 11.9% or 11.3% for <i><b>R</b></i><b>-Phen-Cu-POP</b> or <i><b>S</b></i><b>-Phen-Cu-POP</b>, respectively. Furthermore, the devices displayed efficient circularly polarized electroluminescence (CPEL) with electroluminescence asymmetry factors (<i>g</i><sub>EL</sub>) of +8.7 × 10<sup>–3</sup> and −8.0 × 10<sup>–3</sup> for <i><b>R</b></i><b>/</b><i><b>S</b></i><b>-Phen-Cu-POP</b>.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"62 1","pages":""},"PeriodicalIF":4.7000,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Circularly Polarized Electroluminescence of Chiral Copper(I) Complexes of 1,1’-Binaphthalene-Functionalized 1,10-Phenanthroline\",\"authors\":\"Zhi-Ping Kang, Lin-Xi Shi, Yi-Xin Wei, Jin-Yun Wang, Xu-Yang Ding, Zhong-Ning Chen\",\"doi\":\"10.1021/acs.inorgchem.5c00810\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"This study is dedicated to the design and synthesis of novel yellow-emitting Cu(I) complex enantiomers, <i><b>R</b></i><b>/</b><i><b>S</b></i><b>-Phen-Cu-POP</b>, where the Cu(I) center is chelated by chiral 1,1’-binaphthalene-functionalized 1,10-phenanthroline (Phen) and bis(2-diphenylphosphinophenyl)ether (POP). Photophysical characterization revealed that the quantum yield (<i>Φ</i><sub>em</sub>) of <i><b>R</b></i><b>/</b><i><b>S</b></i><b>-Phen-Cu-POP</b> in CH<sub>2</sub>Cl<sub>2</sub> solutions was only 1.4–1.6%, but it significantly increased to 73.0% (<i><b>R</b></i>) and 76.1% (<i><b>S</b></i>) in PMMA doping films. Circularly polarized luminescence (CPL) studies demonstrated solid-state photoluminescence asymmetry factors (<i>g</i><sub>PL</sub>) of <i><b>R</b></i><b>/</b><i><b>S</b></i><b>-Phen-Cu-POP</b> were +8.5 × 10<sup>–3</sup> and −8.6 × 10<sup>–3</sup>. Temperature-dependent emission spectra and lifetime studies identified a small singlet–triplet energy gap (Δ<i>E</i><sub>ST</sub> = 0.073 eV), which facilitates reverse intersystem crossing (RISC) from the triplet (T<sub>1</sub>) to the singlet (S<sub>1</sub>) state, thus leading to the transformation of phosphorescence at low temperature to thermally activated delayed fluorescence (TADF) at ambient temperature. Solution-processed organic light-emitting diodes (OLEDs) achieved a maximum luminance of 1270 or 1379 cd/m<sup>2</sup>, a current efficiency of 31.8 or 30.3 cd/A, a power efficiency of 14.8 or 14.4 lm/W, and an external quantum efficiency (EQE) of 11.9% or 11.3% for <i><b>R</b></i><b>-Phen-Cu-POP</b> or <i><b>S</b></i><b>-Phen-Cu-POP</b>, respectively. Furthermore, the devices displayed efficient circularly polarized electroluminescence (CPEL) with electroluminescence asymmetry factors (<i>g</i><sub>EL</sub>) of +8.7 × 10<sup>–3</sup> and −8.0 × 10<sup>–3</sup> for <i><b>R</b></i><b>/</b><i><b>S</b></i><b>-Phen-Cu-POP</b>.\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"62 1\",\"pages\":\"\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-04-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.inorgchem.5c00810\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.5c00810","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
本研究致力于设计和合成一种新型的发黄色的Cu(I)络合物对映体R/ s - pheni -Cu-POP,其中Cu(I)中心被手性1,1 ' -联萘功能化的1,10-菲罗啉(Phen)和双(2-二苯基膦苯基)醚(POP)螯合。光物理表征表明,R/S- phenh - cu - pop在CH2Cl2溶液中的量子产率(Φem)仅为1.4-1.6%,而在PMMA掺杂薄膜中的量子产率则显著提高到73.0% (R)和76.1% (S)。圆偏振发光(CPL)研究表明,R/ s - phenh - cu - pop的固态光致发光不对称因子(gPL)分别为+8.5 × 10-3和−8.6 × 10-3。温度依赖的发射光谱和寿命研究发现了一个小的单重态-三重态能隙(ΔEST = 0.073 eV),这有利于从三重态(T1)到单重态(S1)的反向系统间交叉(RISC),从而导致低温磷光向室温热激活延迟荧光(TADF)转变。溶液处理有机发光二极管(oled)的最大亮度为1270或1379 cd/m2,电流效率为31.8或30.3 cd/ a,功率效率为14.8或14.4 lm/W,外部量子效率(EQE)分别为11.9%或11.3%。此外,R/ s - phenh - cu - pop器件显示出高效的圆极化电致发光(CPEL),电致发光不对称因子(gEL)分别为+8.7 × 10-3和−8.0 × 10-3。
Circularly Polarized Electroluminescence of Chiral Copper(I) Complexes of 1,1’-Binaphthalene-Functionalized 1,10-Phenanthroline
This study is dedicated to the design and synthesis of novel yellow-emitting Cu(I) complex enantiomers, R/S-Phen-Cu-POP, where the Cu(I) center is chelated by chiral 1,1’-binaphthalene-functionalized 1,10-phenanthroline (Phen) and bis(2-diphenylphosphinophenyl)ether (POP). Photophysical characterization revealed that the quantum yield (Φem) of R/S-Phen-Cu-POP in CH2Cl2 solutions was only 1.4–1.6%, but it significantly increased to 73.0% (R) and 76.1% (S) in PMMA doping films. Circularly polarized luminescence (CPL) studies demonstrated solid-state photoluminescence asymmetry factors (gPL) of R/S-Phen-Cu-POP were +8.5 × 10–3 and −8.6 × 10–3. Temperature-dependent emission spectra and lifetime studies identified a small singlet–triplet energy gap (ΔEST = 0.073 eV), which facilitates reverse intersystem crossing (RISC) from the triplet (T1) to the singlet (S1) state, thus leading to the transformation of phosphorescence at low temperature to thermally activated delayed fluorescence (TADF) at ambient temperature. Solution-processed organic light-emitting diodes (OLEDs) achieved a maximum luminance of 1270 or 1379 cd/m2, a current efficiency of 31.8 or 30.3 cd/A, a power efficiency of 14.8 or 14.4 lm/W, and an external quantum efficiency (EQE) of 11.9% or 11.3% for R-Phen-Cu-POP or S-Phen-Cu-POP, respectively. Furthermore, the devices displayed efficient circularly polarized electroluminescence (CPEL) with electroluminescence asymmetry factors (gEL) of +8.7 × 10–3 and −8.0 × 10–3 for R/S-Phen-Cu-POP.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.