OLED发光材料的理论计算与分子设计

刘美惠; 彭谦

doi:10.37188/CJL.20220319

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OLED发光材料的理论计算与分子设计

特邀报告 | 更新时间：2023-02-16

- OLED发光材料的理论计算与分子设计增强出版
- Theoretical Calculation and Molecular Design of Light-emitting Materials for OLED
- 发光学报
- 作者机构：
  
  1.中国科学院大学化学科学学院，北京　100049
- 作者简介：
  
  [ "刘美惠（1996-），女，河北秦皇岛人，博士研究生，2021年于首都师范大学获得硕士学位，主要从事弱相互作用对有机光电性能调控的研究。 E-mail： liumeihui21@mails.ucas.ac.cn" ]
  
  刘美惠（1996-），女，河北秦皇岛人，博士研究生，2021年于首都师范大学获得硕士学位，主要从事弱相互作用对有机光电性能调控的研究。 E-mail： liumeihui21@mails.ucas.ac.cn
  [ "彭谦（1978-），女，河南太康县人，博士，教授，博士生导师，2008年于中国科学院化学研究所获得博士学位，主要从事有机光电功能材料理论与计算的研究。" ]
  
  彭谦（1978-），女，河南太康县人，博士，教授，博士生导师，2008年于中国科学院化学研究所获得博士学位，主要从事有机光电功能材料理论与计算的研究。
- 基金信息：
  
  国家自然科学基金(21973099;22273105);中央高校基本科研业务费专项资金
- DOI：10.37188/CJL.20220319 中图分类号： O482.31
- 纸质出版日期：2023-01-05，
  
  收稿日期：2022-09-04，
  
  修回日期：2022-09-25，
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引用本文
刘美惠,彭谦.OLED发光材料的理论计算与分子设计[J].发光学报,2023,44(01):115-128.

LIU Meihui,PENG Qian.Theoretical Calculation and Molecular Design of Light-emitting Materials for OLED[J].Chinese Journal of Luminescence,2023,44(01):115-128.
刘美惠,彭谦.OLED发光材料的理论计算与分子设计[J].发光学报,2023,44(01):115-128. DOI： 10.37188/CJL.20220319.

LIU Meihui,PENG Qian.Theoretical Calculation and Molecular Design of Light-emitting Materials for OLED[J].Chinese Journal of Luminescence,2023,44(01):115-128. DOI： 10.37188/CJL.20220319.

OLED发光材料的理论计算与分子设计 Theoretical Calculation and Molecular Design of Light-emitting Materials for OLED first-author 刘美惠（1996-），女，河北秦皇岛人，博士研究生，2021年于首都师范大学获得硕士学位，主要从事弱相互作用对有机光电性能调控的研究。 E-mail： liumeihui21@mails.ucas.ac.cn http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942004&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942008&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942007&type= 24.89199829 29.88732910 刘美惠（1996-），女，河北秦皇岛人，博士研究生，2021年于首都师范大学获得硕士学位，主要从事弱相互作用对有机光电性能调控的研究。 E-mail： liumeihui21@mails.ucas.ac.cn liumeihui21@mails.ucas.ac.cn corresp corresp E-mail： qianpeng@ucas.ac.cn E-mail： qianpeng@ucas.ac.cn qianpeng@ucas.ac.cn qianpeng@ucas.ac.cn 彭谦（1978-），女，河南太康县人，博士，教授，博士生导师，2008年于中国科学院化学研究所获得博士学位，主要从事有机光电功能材料理论与计算的研究。 http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942010&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942015&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942012&type= 24.89199829 29.88732910 彭谦（1978-），女，河南太康县人，博士，教授，博士生导师，2008年于中国科学院化学研究所获得博士学位，主要从事有机光电功能材料理论与计算的研究。 qianpeng@ucas.ac.cn 中国科学院大学化学科学学院，北京　100049 中国科学院大学化学科学学院，北京　100049 School of Chemical Sciences， University of Chinese Academy of Sciences， Beijing 100049， China School of Chemical Sciences， University of Chinese Academy of Sciences， Beijing 100049， China 数次有机发光二极管（OLED）器件效率的突破均源于有机电致发光新机制的发现和有机发光材料的创新。理论探究有机分子激发态的形成和衰变过程可以加深理解发光的微观机理，促进发光材料分子的研发。本文简要介绍了热振动关联函数（TVCF）的速率理论，及其在荧光、磷光和热激活延迟小分子材料中的应用。针对这三类小分子材料，我们揭示了其发光机理，建立了分子结构与性质之间的关系，提出了表征效率的描述符，并理论设计了优良的OLED发光分子。 Thanks to the discovery of new mechanisms of organic electroluminescence and the innovation of organic light-emitting materials， several breakthroughs have been made in the efficiency of organic light-emitting diode （OLED） device. Theoretical exploration of the formation and decay processes of excited states of organic molecules can deepen the understanding of the mechanism of electroluminescence and boost the development of molecular materials. This review briefly introduces the rate theory of thermal vibration correlation function （TVCF） and its applications in fluorescence， phosphorescence and thermally activated delayed fluorescence small molecular materials. For these three kinds of materials， their light-emitting mechanisms have been revealed， the relationships between molecular structure and properties have been established， the descriptors of efficiencies have been proposed， and then the excellent OLED light-emitting molecules have been designed theoretically from principles. OLED发光材料分子描述符热振动关联函数激发态衰减速率常数发光量子效率 OLED light-emitting materials molecular descriptor thermal vibration correlation function excited state decay rate constant luminescence quantum efficiency 1　引　　言 1 有机发光二极管（OLED）在柔性显示、固态照明、有机激光、化学/生物传感和光通信等高科技领域具有广阔的应用前景，其发展备受科学界和工业界的关注 [ 1 1 - 7 7 1-7 ] 。OLED器件独特的优势很大程度上来源于有机发光材料的多样性、可塑性及可设计性。根据OLED器件的工作原理 [ 8 8 - 9 9 8-9 ] （图1 图1 ）可知，器件的外量子效率（EQE）由4个因素决定 η exe = η rec η exc η pl η oc 。其中 η rec 是载流子形成束缚对的效率，主要取决于半导体中载流子的注入和传输性质； η exc 是发光激子的生成比率，根据自旋量子统计，单线态激子占电生激子总数的25%，三线态激子占75%； η pl 是光致发光量子效率（PLQY）； η oc 是光学耦合常数，即产生的全部光子从器件中出射的比例。由该公式可知，在不考虑光取出的情况下，提高发光材料的 η exc 和 η pl 是提升器件效率的关键。根据激子的利用方式及发展时间进行分类，第一代是传统荧光材料（单线态发光），代表分子如三（8-羟基喹啉）铝（Alq 3 ） [ 10 10 ] ，受自旋统计的限制，激子利用率在理论上不会超过 25%，因此其器件的外量子效率一般不超过5%；第二代是过渡金属配合物磷光材料（三线态发光） [ 11 11 ] ，以铱（Ir）和铂（Pt）配合物为代表 [ 12 12 - 13 13 12-13 ] ，能够依靠重原子效应带来的强自旋轨道耦合（SOC），实现S 1 →T 1 以及T 1 →S 0 的快速系间窜越（ISC）和辐射过程，从而使得激子利用率达到理论值100%，但却存在造价昂贵、色度不全等问题。热活化延迟荧光（TADF）材料是利用反系间窜越（rISC）将三线态转化为单线态，然后单线态发光，其激子利用率理论上可达100%，成为第三代OLED材料，引起了人们的广泛关注 [ 14 14 - 15 15 14-15 ] 。随着OLED材料和器件的发展，人们提出了很多提高激子利用率的新方法和新材料，例如TADF主体材料 [ 16 16 ] 、单线态裂分主体材料 [ 17 17 ] 、单线态裂分-热激子主体材料 [ 18 18 ] 、自由基发光材料 [ 19 19 ] 、热激子-聚集诱导发光材料 [ 20 20 ] 、纯有机室温磷光材料 [ 21 21 - 23 23 21-23 ] 等。中国科学家在这些方面均做了许多原创性工作，为发展具有自主知识产权的市场化发光材料打下基础。一旦激子形成之后，有机分子的发光量子效率取决于激子不同衰减途径之间的竞争。如图2 图2 所示，从激发态（单线态或三线态）到基态有三条衰减途径：（ⅰ）辐射过程（ k r ） [ 24 24 ] ；（ⅱ）在谐振区，由振动弛豫诱导的无辐射衰减过程（NR-VR， k <math id="M1"><msubsup><mrow/><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942025&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942024&type= 2.79399991 4.40266657 ） [ 25 25 ] ；（ⅲ）在非谐振区，通过最小能量交叉点的无辐射衰减过程（NR-MECP， k <math id="M2"><msubsup><mrow/><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">M</mi><mi mathvariant="normal">E</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">P</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942036&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942034&type= 5.24933338 4.40266657 ） [ 26 26 ] 。两种无辐射衰减过程有可能同时存在，并与辐射过程产生竞争。这时，发光量子效率可表示为 η pl = k r /（ k r + k <math id="M3"><msubsup><mrow/><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942033&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942031&type= 2.79399991 4.40266657 + k <math id="M4"><msubsup><mrow/><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">M</mi><mi mathvariant="normal">E</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">P</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942036&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942034&type= 5.24933338 4.40266657 ）。对于有机分子来说，结构比较柔性，发光过程必定伴随着结构变化；但是，是NR-VR还是NR-MECP主导着无辐射过程，长期以来尚未有定论 [ 27 27 - 28 28 27-28 ] 。在NR-VR过程中，分子的几何结构变化相对较小，其速率可以在谐振子模型下进行求解。在NR-MECP过程中，分子的几何结构变化相对较大，或者像图2 图2 所示经过一个过渡态、局部最小点之后上升到MECP点，或者越过一个能垒衰减到MECP点，或者无需能垒衰减到MECP点。对一个实际体系，势能面形状和能垒的高低决定着哪个过程是决速步。从动力学理论的角度来看，无论无辐射衰减是VR还是MECP引起的，非绝热动力学原则上可以给出准确结果。但是，目前非绝热动力学模拟方法的模拟时间是飞秒或皮秒级 [ 29 29 ] ，远小于辐射衰减的纳秒级。这里，我们对于谐振区域采用热振动关联函数（TVCF）速率理论 [ 30 30 - 31 31 30-31 ] ，对于非谐区域采用过渡态理论，对荧光 [ 32 32 ] 、磷光 [ 33 33 ] 、热活化延迟荧光 [ 34 34 - 35 35 34-35 ] 等各种发光材料的激发态衰减速率和发光量子效率进行定量计算，揭示其机理，建立结构-性能关系，提出有效的描述符和分子设计原则，设计出优良性能的发光材料。 2　理论与计算方法 1 基于费米黄金规则和一阶微扰理论，振动弛豫诱导的无辐射速率常数 k nr 可以写作 [ 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http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942108&type= 3.04800010 2.70933342 和 <math id="M18"><mi>Θ</mi></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942115&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942113&type= 2.87866688 2.79399991 分别是电子和振动波函数； <math id="M19"><msub><mrow><mi>ν</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub><mi mathvariant="normal">、</mi><mo> </mo><mo> </mo><msub><mrow><mi>ν</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942120&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942118&type= 7.36600018 4.06400013 分别是初始电子态i和末电子态f的振动态。多重度相同的电子态之间的跃迁被称为内转换，主要由非绝热耦合引起，则有 <math display="block" id="M20"><mfenced open="<" close=">" separators="|"><mrow><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub><msub><mrow><mi>Θ</mi></mrow><mrow><mi mathvariant="normal">f</mi><msub><mrow><mi>ν</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub></mrow></msub><mfenced open="|" close="|" separators="|"><mrow><msup><mrow><mover accent="true"><mi>H</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">B</mi><mi mathvariant="normal">O</mi></mrow></msup></mrow></mfenced><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub><msub><mrow><mi>Θ</mi></mrow><mrow><mi mathvariant="normal">i</mi><msub><mrow><mi>ν</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub></mrow></msub></mrow></mfenced><mo>=</mo><munder><mo movablelimits="false">∑</mo><mrow><mi>k</mi></mrow></munder><mrow><mfenced open="<" close=">" separators="|"><mrow><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub><msub><mrow><mi>Θ</mi></mrow><mrow><mi mathvariant="normal">f</mi><msub><mrow><mi>ν</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub></mrow></msub><mo stretchy="false">|</mo><mo stretchy="false">(</mo><msub><mrow><mover accent="true"><mi>P</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">f</mi><mi mathvariant="normal">k</mi></mrow></msub><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub><mo stretchy="false">)</mo><mo stretchy="false">(</mo><msub><mrow><mover accent="true"><mi>P</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">f</mi><mi mathvariant="normal">k</mi></mrow></msub><msub><mrow><mi>Θ</mi></mrow><mrow><mi mathvariant="normal">i</mi><msub><mrow><mi>ν</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub></mrow></msub><mo stretchy="false">)</mo></mrow></mfenced></mrow></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942126&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942122&type= 75.52266693 7.53533268 ，其中， <math id="M21"><mover accent="true"><mi>P</mi><mo>^</mo></mover></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942131&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942128&type= 2.28600001 3.64066648 是核动量算子，这里忽略小项 <math id="M22"><msup><mrow><mo>∂</mo></mrow><mrow><mn mathvariant="normal">2</mn></mrow></msup><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub><mo>/</mo><mo>∂</mo><msubsup><mrow><mi>Q</mi></mrow><mrow><mi mathvariant="normal">f</mi><mi>l</mi></mrow><mrow><mn mathvariant="normal">2</mn></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942138&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942135&type= 13.71599960 4.91066647 。在谐振子模型和Condon近似下，振动弛豫诱导的内转换速率 <math id="M23"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942147&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942144&type= 4.48733330 4.06400013 可以表示为热振动关联函数的形式： <math display="block" id="M24"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>=</mo><mfrac><mrow><mn mathvariant="normal">1</mn></mrow><mrow><msup><mrow><mi>ћ</mi></mrow><mrow><mn mathvariant="normal">2</mn></mrow></msup></mrow></mfrac><msubsup><mo>∫</mo><mrow><mo>-</mo><mi mathvariant="normal">∞</mi></mrow><mrow><mi mathvariant="normal">∞</mi></mrow></msubsup><mrow><mi mathvariant="normal">d</mi><mi>t</mi></mrow><msup><mrow><mi mathvariant="normal">e</mi></mrow><mrow><mi mathvariant="normal">i</mi><msub><mrow><mi>ω</mi></mrow><mrow><mi mathvariant="normal">i</mi><mi mathvariant="normal">f</mi></mrow></msub><mi>t</mi></mrow></msup><munder><mo movablelimits="false">∑</mo><mrow><mi>k</mi><mo>,</mo><mi>l</mi></mrow></munder><mrow><msubsup><mrow><mi>R</mi></mrow><mrow><mi>k</mi><mi>l</mi></mrow><mrow><mi>N</mi><mi>A</mi><mi>C</mi></mrow></msubsup><msub><mrow><mi>ρ</mi></mrow><mrow><mi>I</mi><mi>C</mi><mo>,</mo><mi>k</mi><mi>l</mi></mrow></msub><mo stretchy="false">(</mo><mi>t</mi><mo>,</mo><mi>T</mi><mo stretchy="false">)</mo></mrow></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942156&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942152&type= 53.17066193 8.55133343 ，其中， <math id="M25"><msubsup><mrow><mi>R</mi></mrow><mrow><mi>k</mi><mi>l</mi></mrow><mrow><mi mathvariant="normal">N</mi><mi mathvariant="normal">A</mi><mi mathvariant="normal">C</mi></mrow></msubsup><mo>=</mo><mo><</mo><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub><mo>∣</mo><msub><mrow><mover accent="true"><mi>P</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">f</mi><mi>k</mi></mrow></msub><mo>∣</mo><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub><mo>></mo><mo><</mo><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub><mo>∣</mo><msub><mrow><mover accent="true"><mi>P</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">f</mi><mi>l</mi></mrow></msub><mo>∣</mo><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub><mo>></mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942161&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942159&type= 46.05867004 5.16466665 是非绝热电子耦合矩阵元； <math id="M26"><msub><mrow><mi>ρ</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">C</mi><mo>,</mo><mi>k</mi><mi>l</mi></mrow></msub><mfenced separators="|"><mrow><mi>t</mi><mo>,</mo><mi>T</mi></mrow></mfenced><mo>=</mo><mi mathvariant="normal">T</mi><mi mathvariant="normal">r</mi><mfenced open="[" close="]" separators="|"><mrow><msubsup><mrow><mi>Z</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow><mrow><mo>-</mo><mn mathvariant="normal">1</mn></mrow></msubsup><msub><mrow><mover accent="true"><mi>P</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">f</mi><mi>k</mi></mrow></msub><msup><mrow><mi mathvariant="normal">e</mi></mrow><mrow><mo>-</mo><mi>i</mi><msub><mrow><mi>τ</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub><msub><mrow><mover accent="true"><mi>H</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub></mrow></msup><msub><mrow><mover accent="true"><mi>P</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">f</mi><mi>l</mi></mrow></msub><msup><mrow><mi mathvariant="normal">e</mi></mrow><mrow><mo>-</mo><mi mathvariant="normal">i</mi><msub><mrow><mi>τ</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub><msub><mrow><mover accent="true"><mi>H</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub></mrow></msup></mrow></mfenced></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942170&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942166&type= 51.13866425 5.75733376 是热振动关联函数，可以通过多维高斯积分进行解析求解 [ 31 31 ] 。同理，多重度不同的电子态之间的系间窜越速率常数 <math id="M27"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942176&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942173&type= 4.65666676 4.06400013 也可以写为热振动关联函数的形式： <math display="block" id="M28"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>=</mo><mfrac><mrow><mn mathvariant="normal">1</mn></mrow><mrow><msup><mrow><mi mathvariant="normal">ℏ</mi></mrow><mrow><mn mathvariant="normal">2</mn></mrow></msup></mrow></mfrac><msubsup><mrow><mi>R</mi></mrow><mrow><mi mathvariant="normal">f</mi><mi mathvariant="normal">i</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">O</mi><mi mathvariant="normal">C</mi></mrow></msubsup><msubsup><mo>∫</mo><mrow><mo>-</mo><mi>∞</mi></mrow><mrow><mi>∞</mi></mrow></msubsup><mrow><mi>d</mi><mi>t</mi><msup><mrow><mi>e</mi></mrow><mrow><mi>i</mi><msub><mrow><mi>ω</mi></mrow><mrow><mi>i</mi><mi>f</mi></mrow></msub><mi>t</mi></mrow></msup><msub><mrow><mi>ρ</mi></mrow><mrow><mi>I</mi><mi>S</mi><mi>C</mi></mrow></msub><mo stretchy="false">(</mo><mi>t</mi><mo>,</mo><mi>T</mi><mo stretchy="false">)</mo></mrow></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942182&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942178&type= 47.15933609 7.70466709 ，其中， <math id="M29"><msubsup><mrow><mi>R</mi></mrow><mrow><mi mathvariant="normal">f</mi><mi mathvariant="normal">i</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">O</mi><mi mathvariant="normal">C</mi></mrow></msubsup><mo>=</mo><msup><mrow><mfenced open="|" close="|" separators="|"><mrow><mfenced open="<" close=">" separators="|"><mrow><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub><mfenced open="|" close="|" separators="|"><mrow><msup><mrow><mover accent="true"><mi>H</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">O</mi></mrow></msup></mrow></mfenced><msub><mrow><mi>Φ</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub></mrow></mfenced></mrow></mfenced></mrow><mrow><mn mathvariant="normal">2</mn></mrow></msup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942188&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942184&type= 33.78200150 7.87400007 是自旋轨道耦合矩阵元； <math id="M30"><msub><mrow><mi>ρ</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow></msub><mo stretchy="false">(</mo><mi>t</mi><mo>,</mo><mi>T</mi><mo stretchy="false">)</mo><mo>=</mo><mi mathvariant="normal">T</mi><mi mathvariant="normal">r</mi><mfenced open="[" close="]" separators="|"><mrow><msup><mrow><mi mathvariant="normal">e</mi></mrow><mrow><mo>-</mo><mi mathvariant="normal">i</mi><msub><mrow><mi>τ</mi></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub><msub><mrow><mover accent="true"><mi>H</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">f</mi></mrow></msub></mrow></msup><msup><mrow><mi mathvariant="normal">e</mi></mrow><mrow><mo>-</mo><mi mathvariant="normal">i</mi><msub><mrow><mi>τ</mi></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub><msub><mrow><mover accent="true"><mi>H</mi><mo>^</mo></mover></mrow><mrow><mi mathvariant="normal">i</mi></mrow></msub></mrow></msup></mrow></mfenced></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942193&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942191&type= 37.84600067 5.41866684 是热振动关联函数，其求解过程见文献[ 39 39 ]。有限温度下，自发辐射速率常数是对发射光谱在全波段范围内的积分： <math display="block" id="M31"><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow></msub><mo>=</mo><mo>∫</mo><msub><mrow><mi>σ</mi></mrow><mrow><mi mathvariant="normal">e</mi><mi mathvariant="normal">m</mi><mi mathvariant="normal">i</mi></mrow></msub><mo stretchy="false">(</mo><mi>ω</mi><mo>,</mo><mi>T</mi><mo stretchy="false">)</mo><mi mathvariant="normal">d</mi><mi>ω</mi></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942199&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942196&type= 29.37933159 6.43466663 ，其中，发射光谱： <math display="block" id="M32"><msub><mrow><mi>σ</mi></mrow><mrow><mi mathvariant="normal">e</mi><mi mathvariant="normal">m</mi></mrow></msub><mo stretchy="false">(</mo><mi>ω</mi><mo>,</mo><mi>T</mi><mo stretchy="false">)</mo><mo>=</mo><mfrac><mrow><mn mathvariant="normal">2</mn><msup><mrow><mi>ω</mi></mrow><mrow><mn mathvariant="normal">3</mn></mrow></msup></mrow><mrow><mn mathvariant="normal">3</mn><mi mathvariant="normal">π</mi><mi mathvariant="normal">ℏ</mi><msup><mrow><mi>c</mi></mrow><mrow><mn mathvariant="normal">3</mn></mrow></msup></mrow></mfrac><msup><mrow><mfenced open="|" close="|" separators="|"><mrow><mi>μ</mi></mrow></mfenced></mrow><mrow><mn mathvariant="normal">2</mn></mrow></msup><msubsup><mo>∫</mo><mrow><mo>-</mo><mi mathvariant="normal">∞</mi></mrow><mrow><mi mathvariant="normal">∞</mi></mrow></msubsup><mrow><mi mathvariant="normal">d</mi><mi>t</mi></mrow><msup><mrow><mi mathvariant="normal">e</mi></mrow><mrow><mo>-</mo><mi mathvariant="normal">i</mi><mfenced separators="|"><mrow><mi>ω</mi><mo>-</mo><msub><mrow><mi>ω</mi></mrow><mrow><mi mathvariant="normal">i</mi><mi mathvariant="normal">f</mi></mrow></msub></mrow></mfenced><mi>t</mi></mrow></msup><msub><mrow><mi>ρ</mi></mrow><mrow><mi mathvariant="normal">e</mi><mi mathvariant="normal">m</mi></mrow></msub><mo stretchy="false">(</mo><mi>t</mi><mo>,</mo><mi>T</mi><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942203&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942201&type= 70.35800171 7.87400007 ， <math id="M33"><mi>μ</mi></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942211&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942206&type= 2.37066650 3.38666677 是跃迁偶极矩矩阵元， <math id="M34"><msub><mrow><mi>ρ</mi></mrow><mrow><mi mathvariant="normal">e</mi><mi mathvariant="normal">m</mi></mrow></msub><mo stretchy="false">(</mo><mi>t</mi><mo>,</mo><mi>T</mi><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942216&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942214&type= 12.44600010 4.65666676 与 <math id="M35"><msub><mrow><mi>ρ</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow></msub><mo stretchy="false">(</mo><mi>t</mi><mo>,</mo><mi>T</mi><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942221&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942218&type= 12.95400047 4.65666676 形式相同，求解方法相同。对于非谐振区，过程 <math id="M36"><mi mathvariant="normal">E</mi><mi mathvariant="normal">S</mi><munder><mrow><mover accent="false"><mo>⇌</mo><mrow><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">a</mi></mrow></msub></mrow></mover></mrow><mrow><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">b</mi></mrow></msub></mrow></munder><mi mathvariant="normal">M</mi><mi mathvariant="normal">E</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">P</mi><mover accent="false"><mo>→</mo><mrow><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">c</mi></mrow></msub></mrow></mover><msub><mrow><mi mathvariant="normal">S</mi></mrow><mrow><mn mathvariant="normal">0</mn></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942227&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942224&type= 34.29000092 7.28133297 的速率常数 <math id="M37"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">M</mi><mi mathvariant="normal">E</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">P</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942405&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942402&type= 6.85799980 4.06400013 可表示为： <math display="block" id="M38"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">M</mi><mi mathvariant="normal">E</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">P</mi></mrow></msubsup><mo>=</mo><mfrac><mrow><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">c</mi></mrow></msub><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">a</mi></mrow></msub></mrow><mrow><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">c</mi></mrow></msub><mo>+</mo><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">b</mi></mrow></msub></mrow></mfrac><mo>=</mo><msub><mrow><mi>A</mi></mrow><mrow><mn mathvariant="normal">0</mn></mrow></msub><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">a</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942246&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942240&type= 32.85066605 8.04333401 ，其中 <math id="M39"><msub><mrow><mi>A</mi></mrow><mrow><mn mathvariant="normal">0</mn></mrow></msub><mo>=</mo><mn mathvariant="normal">1</mn><mo>/</mo><mo stretchy="false">[</mo><mn mathvariant="normal">1</mn><mo>+</mo><mi mathvariant="normal">e</mi><mi mathvariant="normal">x</mi><mi mathvariant="normal">p</mi><mo stretchy="false">(</mo><mfrac><mrow><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">c</mi></mrow></msub><mo>-</mo><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">b</mi></mrow></msub></mrow><mrow><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">B</mi></mrow></msub><mi>T</mi></mrow></mfrac><mo stretchy="false">)</mo><mo stretchy="false">]</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942257&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942251&type= 42.16400146 7.95866632 （ E b 和 E c 是电子能量势垒）， <math id="M40"><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">a</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942267&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942262&type= 2.70933342 3.72533321 可由过渡态理论计算得到： <math display="block" id="M41"><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">a</mi></mrow></msub><mo>=</mo><mfrac><mrow><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">B</mi></mrow></msub><mi>T</mi></mrow><mrow><mi>h</mi></mrow></mfrac><mi mathvariant="normal">e</mi><mi mathvariant="normal">x</mi><mi mathvariant="normal">p</mi><mfenced separators="|"><mrow><mo>-</mo><mfrac><mrow><mi mathvariant="normal">Δ</mi><msup><mrow><mi>G</mi></mrow><mrow><mo>≠</mo></mrow></msup></mrow><mrow><mi>R</mi><mi>T</mi></mrow></mfrac></mrow></mfenced></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942277&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942272&type= 31.24200058 8.97466660 ，其中， <math id="M42"><mi mathvariant="normal">Δ</mi><msup><mrow><mi>G</mi></mrow><mrow><mo>≠</mo></mrow></msup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942286&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942282&type= 5.92666674 3.04800010 表示在 <math id="M43"><mmultiscripts><mrow/><mprescripts/><mrow/><mrow><mn mathvariant="normal">3</mn></mrow></mmultiscripts><mi mathvariant="normal">E</mi><mi mathvariant="normal">S</mi></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942294&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942290&type= 5.58799982 3.55599999 和 <math id="M44"><mmultiscripts><mrow/><mprescripts/><mrow/><mrow><mn mathvariant="normal">3</mn></mrow></mmultiscripts><mi mathvariant="normal">M</mi><mi mathvariant="normal">E</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">P</mi></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942303&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942298&type= 10.83733368 3.55599999 之间的吉布斯自由能。利用以上理论公式，结合量子化学，定量计算各种发光材料在不同环境下的发光量子效率。这里，分别采用连续极化模型（PCM）和量子力学/分子力学方法（QM/MM）来考虑溶液和聚集环境。量化计算单个分子激发态采用TD-DFT方法。在本文中，我们选择两种方法进行QM/MM计算，一种是使用CHEMSHELL 3.5接口程序 [ 40 40 ] ，其中的QM计算使用TURBOMOLE 6.5程序包 [ 41 41 ] ，MM使用DL_POLY程序包 [ 42 42 ] ；另一种是使用Gaussian 16中的ONIOM方法。SOC通过PySOC软件包 [ 43 43 ] 或者ORCA程序包 [ 44 44 ] 计算。MECP的优化在sobMECP程序包中完成 [ 43 43 ] 。辐射与无辐射速率常数通过MOMAP 程序包计算 [ 45 45 ] 。 3　发光机理与分子设计 1 3.1　荧光体系 2 荧光材料因其成本低、稳定、色纯度高仍在OLED材料中占有一席之地，特别是蓝光发光材料。由OLED工作原理可知，有机分子通常在聚集态和固态下发光。相较于溶液中的“自由”分子，处于“限域”环境下的分子可以表现出完全不同的光响应行为。例如，在溶液中强发光体系的刚性共轭平面分子，在聚集态下会发生荧光猝灭；而在溶液中无发光或者弱发光的柔性体系，在聚集状态下发出强光。我们结合量化方法，应用TVCF速率理论，定量计算了各种荧光体系（图3 图3 ）在气相、溶液和固态等不同环境下的荧光量子效率，并与实验测量值进行了比较（图4 图4 （a））。这里， <math id="M45"><mo> </mo><mi>η</mi><msubsup><mrow><mo> </mo></mrow><mrow><mi mathvariant="normal">F</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>=</mo><mrow><mrow><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mtext> </mtext></mrow></msub></mrow><mo>/</mo><mrow><mo stretchy="false">(</mo><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow></msub><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo stretchy="false">)</mo></mrow></mrow></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942308&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942306&type= 29.71800041 4.14866638 ，只考虑了辐射衰减和振动弛豫诱导的无辐射跃迁。由图4 图4 （a）可以看出，计算值与实验值吻合很好，这说明：（1）量化方法和TVCF方法对振动弛豫诱导的无辐射速率的描述是可靠的；（2）在这些体系中，忽略MECP诱导的无辐射衰减是合理的。由图4 图4 （a）可以看到，分子 19 、 27 、 32 及 40 在溶液中的荧光量子效率很低，而在聚集状态下提高，表现出聚集诱导或者增强发光现象。经过对比分析两种环境下的激发态性质和衰减速率常数，我们发现，分子聚集可以削弱电子与多种不同类型的振动（包括环旋转 [ 46 46 ] 、键弯曲 [ 47 47 ] 和键摇摆 [ 48 48 ] ）之间的耦合及振动-振动之间的耦合（图4 图4 （b）），急剧减慢无辐射跃迁，使得辐射跃迁占主导，致使荧光增强。电子-振动耦合/振动-振动耦合对环境的敏感性可以通过实验可测的瞬态共振拉曼光谱和同位素效应进行验证 [ 25 25 , 49 49 ] 。最重要的是，我们可以将电子-振动耦合投影到分子内坐标上，能够清晰地勾勒出电子-振动耦合和振动-振动耦合所在的化学结构片段，以此提出了分子化学结构的片段改造、移除、重组及改变分子的聚集结构和周围环境等手段来达到解耦合的化学结构策略，有助于设计高效发光的固态荧光体系 [ 32 32 ] 。 3.2　磷光体系 2 金属有机配合物磷光材料由于高的激子利用率成为第二代 OLED发光材料。其中，Pt（Ⅱ）配合物因具有短寿命和高效率而备受关注 [ 50 50 - 51 51 50-51 ] 。目前，商业化的磷光材料仅限于绿光和红光，蓝光器件的稳定性和效率滚降问题尚未得到有效解决。所以，高效的深蓝光磷光材料亟待研发。最近，对蓝光Pt（Ⅱ）配合物的研究发展迅猛，其磷光效率已经接近100%，并且磷光寿命在室温下是微妙级别 [ 52 52 - 53 53 52-53 ] 。Pt（Ⅱ）配合物具有二齿配体、三齿配体、四齿配体等多种配体结构，表现出丰富的化学结构和光物理性质 [ 54 54 - 55 55 54-55 ] 。而且，在四齿配体中，不同的环金属配体也能形成不同的平面或者扭曲结构，导致迥异的发光性质 [ 56 56 - 57 57 56-57 ] 。但是，Pt（Ⅱ）配合物具有不饱和的d轨道，容易形成金属中心（ 3 MC）态，猝灭发光。为了考查Pt（Ⅱ）配合物的结构-性能关系，我们选择16个5/6/6金属环四齿配体Pt（Ⅱ）配合物（图5 图5 ） [ 58 58 - 61 61 58-61 ] ，应用TVCF和过渡态理论，系统地研究了其磷光辐射速率、振动弛豫诱导的无辐射速率和MECP诱导的无辐射速率及磷光量子效率 [ 33 33 ] 。图6 图6 （a）比较了计算和实验的磷光量子效率 <math id="M48"><mo> </mo><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">P</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942367&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942364&type= 3.72533321 4.48733330 ，其中， <math id="M49"><mo> </mo><msubsup><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">P</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>=</mo><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow></msub><mo>/</mo><mo stretchy="false">(</mo><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow></msub><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942374&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942370&type= 28.53266525 4.99533367 ， <math id="M50"><mo> </mo><msubsup><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">P</mi></mrow><mrow><mi mathvariant="normal">t</mi><mi mathvariant="normal">o</mi><mi mathvariant="normal">t</mi></mrow></msubsup><mo>=</mo><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow></msub><mo>/</mo><mo stretchy="false">(</mo><msub><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow></msub><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">M</mi><mi mathvariant="normal">E</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">P</mi></mrow></msubsup><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942380&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942378&type= 39.20066452 4.99533367 。由图6 图6 （a）可知，分子 44 的 <math id="M51"><mo> </mo><msubsup><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">P</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942391&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942388&type= 5.24933338 4.74133301 偏离实验值。分子 44 具有能垒较低的 3 MC态和MECP，其余分子的 <math id="M52"><mo> </mo><msubsup><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">P</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942391&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942388&type= 5.24933338 4.74133301 与 <math id="M53"><mo> </mo><msubsup><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">P</mi></mrow><mrow><mi mathvariant="normal">t</mi><mi mathvariant="normal">o</mi><mi mathvariant="normal">t</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942399&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942395&type= 4.65666676 4.74133301 几乎重叠，并与实验值高度吻合。这表明它们具有难以到达的 3 MC态和MECP，同时证明了TVCF速率理论定量预测Pt（Ⅱ）配合物的磷光量子效率的可靠性。图6 图6 （b）是分子 44 的势能面，稳定态 3 ES沿着Pt—N配位键的断裂方向，越过较小能垒（ E a =0.41 eV， E b =0.01 eV， E c =0.30 eV）的 3 TS到达 3 MC态，之后借助于温度效应热分布到MECP，快速回到S 0 。而且，根据公式（8）公式（8）和公式（9）公式（9），由于分子 44 具有较小的吉布斯自由能， k a 达到10 10 s -1 ，得到 <math id="M54"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">M</mi><mi mathvariant="normal">E</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">P</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942405&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942402&type= 6.85799980 4.06400013 （8.06×10 5 s -1 ）与 <math id="M55"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">V</mi><mi mathvariant="normal">C</mi><mi mathvariant="normal">F</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942411&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942408&type= 6.51933336 4.06400013 （4.75×10 5 s -1 ）形成竞争关系。相较于其他体系，在Pt—N的邻位上引入的两个—CH 3 的位阻效应活化了Pt—N配位键，导致 3 MC生成。从图6 图6 （a）还可以看出，没有 3 MC生成，分子 54~56 的磷光效率也比较低。我们进一步分析了决定结构弛豫诱导的无辐射跃迁速率的重要参数重整能（图6 图6 （c ））。分子 54~56 的重整能远大于其他体系的重整能。再从重整能对内坐标的投影结果来看（图6 图6 （d）），增加的重整能主要来源于咔唑，柔性取代基的引入活化了咔唑。总之，通过TVCF和过渡态理论，定量预测了蓝光四齿配体Pt（Ⅱ）配合物的磷光量子效率，建立了结构-性能关系，为设计出高效的蓝光Pt（Ⅱ）配合物提供了思路。例如，移除Pt—N的邻位的取代基，避免 3 MC的生成；移除咔唑外围上的柔性基团，避免大的结构弛豫引起的无辐射跃迁。 3.3　热活化延迟荧光体系 2 TADF体系由于高稳定性和高激子利用率成为第三代OLED发光材料，具有很大的商业潜力 [ 62 62 - 64 64 62-64 ] 。在TADF机理中，电注入形成的三线态激子通过rISC过程转化为单线态激子，从而发射荧光。所以，TADF是否发生取决于rISC的速率。人们公认的就是减少单线态-三线态能隙（ <math id="M64"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 ），增加SOC，来提高rISC速率。由此可知，在保证 <math id="M65"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 足够小的条件下，引入重原子会大大增强SOC，加快rISC（10 8 ~10 10 s -1 ）速率并提高TADF效率 [ 65 65 - 67 67 65-67 ] 。但是，最近的实验报道的两个具有TADF性质的Au（Ⅲ）配合物 [ 68 68 - 69 69 68-69 ] （如图7 图7 （a）的 57 和 58 ），配合物 57 的 <math id="M66"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942611&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942610&type= 5.67266655 4.06400013 ∼10 10 s -1 ，TADF效率（ <math id="M67"><mo> </mo><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">A</mi><mi mathvariant="normal">D</mi><mi mathvariant="normal">F</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942572&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942571&type= 7.45066643 4.48733330 ）为79%；配合物 58 的 <math id="M68"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942611&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942610&type= 5.67266655 4.06400013 ∼10 7 s -1 而 <math id="M69"><mo> </mo><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">A</mi><mi mathvariant="normal">D</mi><mi mathvariant="normal">F</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942572&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942571&type= 7.45066643 4.48733330 高达94%，这明显与减小 <math id="M70"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 加快rISC来提高TADF效率的观点不符。所以，我们不能像对待纯有机体系那样，只用 <math id="M71"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 来判断TADF效率的高低。于是，我们应用量化方法和TVCF速率理论详细计算了配合物的 <math id="M72"><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">A</mi><mi mathvariant="normal">D</mi><mi mathvariant="normal">F</mi></mrow></msub><mo>=</mo><mfenced open="[" close="]" separators="|"><mrow><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow></msub><mo>⋅</mo><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow></msub><mo>/</mo><mo stretchy="false">(</mo><mn mathvariant="normal">1</mn><mo>-</mo><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow></msub><mo>⋅</mo><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow></msub><mo stretchy="false">)</mo></mrow></mfenced><mo>⋅</mo><msubsup><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">F</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942493&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942491&type= 60.45199966 4.48733330 ， <math id="M73"><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow></msub><mo>=</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942496&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942494&type= 7.95866632 4.48733330 <math display="block" id="M74"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>/</mo><mo stretchy="false">(</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">S</mi></mrow></msubsup><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942500&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942498&type= 31.15733528 4.82600021 ， <math display="block" id="M75"><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow></msub><mo>=</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>/</mo><mo stretchy="false">(</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">T</mi></mrow></msubsup><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942504&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942502&type= 42.58732986 4.99533367 ， <math id="M76"><msubsup><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">F</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>=</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup><mo>/</mo><mo stretchy="false">(</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup><mo>+</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">S</mi></mrow></msubsup><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942507&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942506&type= 39.62400055 4.99533367 （表1 表1 ）。其中， <math id="M77"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942596&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942595&type= 3.13266683 4.06400013 和 <math id="M78"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">S</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942511&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942510&type= 6.43466663 4.06400013 分别是S 1 →S 0 的辐射和无辐射速率常数， <math id="M79"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942513&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942512&type= 3.21733332 4.06400013 和 <math id="M80"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942533&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942532&type= 6.51933336 4.06400013 分别是T 1 →S 0 的辐射和无辐射速率常数， <math id="M81"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942517&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942516&type= 4.99533367 4.06400013 和 <math id="M82"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942521&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942520&type= 5.67266655 4.06400013 分别是S 1 ↔T 1 的系间窜越和反系间窜越速率常数。从分子 57 和 58 的计算结果我们发现，除了 <math id="M83"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942521&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942520&type= 5.67266655 4.06400013 不同， 57 的 <math id="M84"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942533&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942532&type= 6.51933336 4.06400013 ~10 6 s -1 要比分子 58 的 <math id="M85"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942533&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942532&type= 6.51933336 4.06400013 ~10 4 s -1 大两个数量级，从而导致前者的TADF效率偏低。这表明在金属有机配合物中，TADF效率不仅与 <math id="M86"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942527&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942526&type= 7.28133297 3.89466691 有关，更依赖于 <math id="M87"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942531&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942530&type= 6.51933336 4.06400013 的大小。为了分析 <math id="M88"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942531&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942530&type= 6.51933336 4.06400013 的来源，图7 图7 （b）给出了两个配合物的重整能的分布图，相对于配合物 57，配合物 58 中的O原子桥连的四齿配体骨架限制了结构扭转变化，大大减小了重整能，致使 <math id="M89"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942533&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942532&type= 6.51933336 4.06400013 减小了两个数量级。因此，我们可以通过引入O原子或者亚甲基构建六元环，以此增强体系刚性，保持较小的T 1 →S 0 无辐射速率，进而得到高效率的TADF分子。 <math id="M98"><mo/><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942556&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942555&type= 2.70933342 3.47133350 <math id="M99"><mo/><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942558&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942557&type= 3.30200005 3.47133350 <math id="M100"><mo/><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942560&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942559&type= 2.79399991 3.47133350 <math id="M101"><mo/><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942562&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942561&type= 3.30200005 3.47133350 <math id="M102"><mo/><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942564&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942563&type= 4.40266657 3.47133350 <math id="M103"><mo/><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942566&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942565&type= 4.91066647 3.47133350 <math id="M104"><mo/><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">A</mi><mi mathvariant="normal">D</mi><mi mathvariant="normal">F</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942568&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942567&type= 6.51933336 3.89466691 57 6.50×10 6 3.04×10 4 2.75×10 3 1.18×10 6 2.21×10 10 1.47×10 10 0.78（0.79）［ 68 68 ］ 58 3.19×10 7 6.60×10 4 1.80×10 3 9.70×10 3 5.05×10 8 2.00×10 7 0.93（0.94）［ 69 69 ］基于以上得到的结构-性能关系，我们设计了一系列配合物 59~67 ，计算的 <math id="M105"><mo> </mo><msub><mrow><mi>η</mi></mrow><mrow><mi mathvariant="normal">T</mi><mi mathvariant="normal">A</mi><mi mathvariant="normal">D</mi><mi mathvariant="normal">F</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942572&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942571&type= 7.45066643 4.48733330 、 <math id="M106"><mo> </mo><mi mathvariant="normal">l</mi><mi mathvariant="normal">g</mi><mo stretchy="false">(</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942574&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942573&type= 13.46199989 5.07999992 、 <math id="M107"><mo> </mo><mi mathvariant="normal">l</mi><mi mathvariant="normal">g</mi><mo stretchy="false">(</mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup><mo stretchy="false">)</mo></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942576&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942575&type= 12.61533356 5.07999992 以及 <math id="M108"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 见图7 图7 （c）。这些配合物的TADF 效率被预测在94%~99%。这是因为通过调控取代基的给受电子能力，或者将四齿配体变成C^C^C^N和C^N^C^C，促进HOMO和LUMO轨道的分离，保持较小的 <math id="M109"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 。在该前提下，减小 <math id="M110"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942582&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942581&type= 6.51933336 4.06400013 会进一步提高TADF效率。配合物 67 的TADF效率最高，甚至达到99%。该工作将对未来的理论和实验相关工作提供有意义的指导作用。众所周知，在有机体系中，小的 <math id="M111"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 是实现TADF的前提条件。根据量子化学理论， <math id="M112"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942586&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942585&type= 7.28133297 3.89466691 主要与HOMO和LUMO之间的重叠积分成正比，HOMO和LUMO轨道之间的分离会导致小的 <math id="M113"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 。因此，采用给体-受体（D-A）结构，形成具有电荷转移（CT）特征的激发态是获得TADF材料分子的最有效途径 [ 70 70 - 72 72 70-72 ] 。以此，大量的具有较强的分子内CT、分子间CT以及空间/键共轭 CT 的TADF材料分子被合成和研究 [ 73 73 - 78 78 73-78 ] 。但是，小的轨道重叠不可避免地使跃迁偶极矩减小，相应地导致较小的辐射速率和受激发射截面（ <math id="M114"><msub><mrow><mi>σ</mi></mrow><mrow><mi mathvariant="normal">e</mi><mi mathvariant="normal">m</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942598&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942597&type= 4.91066647 3.72533321 ） [ 79 79 - 80 80 79-80 ] ，极大限制了TADF材料的应用。最近，Hatakeyama等提出了具有大振子强度的多重共振热激活延迟荧光（MR-TADF）材料，其中缺电子原子和富电子原子相反地排列在刚性的多环芳香骨架上，通过多重共振效应使得HOMO和LUMO有效分离，进而产生TADF所需的小 <math id="M115"><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942592&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942591&type= 7.02733374 3.89466691 [ 81 81 ] 。但是，由于MR-TADF 材料通常具有较小的rISC速率和斯托克斯位移，这会导致自吸收和湮灭，不利于产生有机激光。因此，在TADF分子中同时实现大的 <math id="M116"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942594&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942593&type= 5.33400011 4.06400013 、 <math id="M117"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942596&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942595&type= 3.13266683 4.06400013 和 <math id="M118"><msub><mrow><mi>σ</mi></mrow><mrow><mi mathvariant="normal">e</mi><mi mathvariant="normal">m</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942598&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942597&type= 4.91066647 3.72533321 是一个挑战性难题 [ 82 82 ] 。这方面已经有一些很优秀的工作，例如，乔娟、彭谦等通过J型Frenkel激子与CT激子的耦合来同时得到快的 <math id="M119"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942613&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942612&type= 2.87866688 4.06400013 和较小的 <math id="M120"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 ，在近红外区域实现了高效的TADF [ 83 83 ] 。马於光、杨兵等提出具有局域-电荷转移杂化激发态（HLCT）的热激子机制，在确保有效rISC的前提下又有较快的辐射衰减 [ 84 84 ] ，取得了很好的效果。这里，我们提出了一种新策略：对于具有局域跃迁（LE）特征的S 1 和T 1 的分子，在保持S 1 的LE特性和大 <math id="M121"><mo> </mo><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942604&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942603&type= 7.28133297 3.89466691 的前提下，调节更高三线态（如T 2 ）来调控S-T之间的转化，实现局域发光态的TADF（LE-TADF）。基于这个策略，我们利用具有不同电负性的取代基（—NO 2 、—CH 3 和—NH 2 ）来调节二氟化硼衍生物（图8 图8 ）的激发态，成功地通过LE/CT组分的比例调节了T 2 能级及其与S 1 之间的转化，同时保持了LE特性的S 1 及其与T 1 之间的大能隙。图8 图 8 给出了各种取代后二氟化硼衍生物的激发态性质、态之间的自旋轨道耦合常数及激发态的衰减和相互转化速率。由图8 图8 可知，随着取代基给电子能力从S-NO 2 、S-CH 3 到S-NH 2 增强，T 2 的电子跃迁性质从CT、HLCT到LE的变化，其能级正像我们期待的从低于S 1 到逐渐靠近S 1 最后高于S 1 ，T 2 -T 1 的能级差随之变大，这表明三者将会表现出不同的激发态转化和发光行为。图8 图8 中数据显示，相对于常见的碳氢体系的弱SOC（ < 1.0 cm -1 ），这三种体系的SOC都比较大，有利于单重态与三重态之间的转化。我们进一步通过TVCF方法结合MOMAP 程序定量评估了各个过程的跃迁速率。对于S-NO 2 ，S 1 →T 2 →T 1 的转换速率很快，并且T 2 →T 1 的 <math id="M122"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">I</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942609&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942608&type= 4.74133301 4.06400013 比T 2 →S 1 的 <math id="M123"><mo> </mo><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi><mi mathvariant="normal">I</mi><mi mathvariant="normal">S</mi><mi mathvariant="normal">C</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942611&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942610&type= 5.67266655 4.06400013 大两个数量级，这明显有利于T 1 的生成。因此，实验中S-NO 2 只发射磷光 [ 85 85 ] 。对于S-NH 2 ，具有相当的辐射和无辐射速率常数，我们预测表现出荧光。令人兴奋的是，对于S-CH 3 ，S 1 →S 0 的 <math id="M124"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">S</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942613&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942612&type= 2.87866688 4.06400013 是传统荧光的典型值，并且比普通TADF（~10 6 s -1 ）大两个数量级 [ 86 86 - 87 87 86-87 ] ，S 1 ↔T 2 →T 1 间较快的相互转换表现出动态平衡分布。计算结果表明TADF来自LE态。到目前为止，无论从能级角度还是从动力学角度均定量预测了LE态的TADF。我们合成了S-CH 3 ，并得到其光谱发射位置随着溶剂极性增加变化很小，证明了S 1 态的跃迁性质与溶剂极性无关，没有CT或HLCT的溶液极性依赖特征 [ 34 34 ] 。理论预测和实验结果均证明，该化合物是一种很有前途的有机材料放大自发辐射材料。基于以上结果，通过我们提出的分子设计策略，在二氟化硼衍生物中引入中性的甲基，保持S 1 的LE特征，通过调控T 2 性质与具有LE特性的S 1 之间的快速ISC/rISC过程，得到非D-A型结构的LE-TADF，这为高效率的TADF发展了提供了新的设计思路。 4　总结与展望 1 本综述针对荧光、金属配合物磷光、TADF材料，通过TVCF速率理论结合量化计算定量描述了有机体系的发光量子效率，揭示其发光理论，并提出高效发光的设计策略。我们提出的TVCF速率理论适合于大多数分子发光体系，但是不同的发光体系有着不同的发光机理。各类发光材料的结构设计着重于以下几个方面：（1）对于荧光体系，我们根据分子内坐标对电子-振动耦合的贡献，有针对性地改造、移除及重组分子片段来解开强烈的电子-振动耦合，从而减缓无辐射速率，增强荧光。（2）对于蓝光Pt（Ⅱ）配合物体系，选择合适的配体，避免 3 MC的生成；增强配体的刚性，避免大的结构弛豫，减慢无辐射跃迁。（3）对于热活化延迟荧光体系，含金属的TADF分子，除了有较小的 <math id="M125"><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942615&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942614&type= 7.02733374 3.89466691 ，必须增强体系刚性，保持小的 <math id="M126"><msubsup><mrow><mi>k</mi></mrow><mrow><mi mathvariant="normal">n</mi><mi mathvariant="normal">r</mi></mrow><mrow><mi mathvariant="normal">V</mi><mi mathvariant="normal">R</mi><mi mathvariant="normal">⁃</mi><mi mathvariant="normal">T</mi></mrow></msubsup></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942617&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942616&type= 6.18066692 4.06400013 ，才能得到高效率的TADF。对于纯有机TADF，通过分子设计，完全可以实现LE-TADF [ 88 88 - 89 89 88-89 ] 。对于具有LE特征的S 1 和T 1 的分子，在保持S 1 的LE特性和大 <math id="M127"><mi mathvariant="normal">Δ</mi><msub><mrow><mi>E</mi></mrow><mrow><mi mathvariant="normal">S</mi><mi mathvariant="normal">T</mi></mrow></msub></math> http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942619&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=39942618&type= 7.02733374 3.89466691 的前提下，通过具有中等电负性的—CH 3 调节更高三线态（如T 2 ）来调控S-T之间的转化，从而在没有典型D-A型结构的分子体系中实现LE-TADF。至此，我们的理论工作不仅能合理解释诸多实验现象，还能够提出相应的分子设计策略，预测出高性能的OLED发光材料。随着有机发光领域的系列突破性进展，新现象、新概念、新机理和新材料不断涌现，这给理论带来了很大的机遇和挑战。比如，如何实现激子利用率突破200%问题？如何理解有机共轭体系中的最低三重态高于单重态？如何设计三重态高于单重态的分子体系？如何解释有机分子在聚集状态下多重发射现象？如何设计和实现高效的深蓝光体系？等等，这些问题尚待解决。我们一直在追求探索新模型、新理论和新方法的路上，期望可以为推动我国OLEDs产业的发展做出贡献。参考文献 MA W B ， SU Y R ， ZHANG Q S ， et al . Thermally activated delayed fluorescence （TADF） organic molecules for efficient X-ray scintillation and imaging ［J］. Nat. Mater. ， 2022 ， 21 （ 2 ）： 210 - 216 . doi: 10.1038/s41563-021-01132-x http://dx.doi.org/10.1038/s41563-021-01132-x Thermally activated delayed fluorescence （TADF） organic molecules for efficient X-ray scintillation and imaging GAO R ， KODAIMATI M S ， YAN D P . Recent advances in persistent luminescence based on molecular hybrid materials ［J］. Chem. Soc. Rev. ， 2021 ， 50 （ 9 ）： 5564 - 5589 . doi: 10.1039/d0cs01463j http://dx.doi.org/10.1039/d0cs01463j Recent advances in persistent luminescence based on molecular hybrid materials HONG G ， GAN X M ， LEONHARDT C ， et al . A brief history of OLEDs-emitter development and industry milestones ［J］. Adv. Mater. ， 2021 ， 33 （ 9 ）： 2005630-1-24 . doi: 10.1002/adma.202005630 http://dx.doi.org/10.1002/adma.202005630 A brief history of OLEDs-emitter development and industry milestones LI Q Q ， LI Z . Molecular packing： another key point for the performance of organic and polymeric optoelectronic materials ［J］. Acc. Chem. Res. ， 2020 ， 53 （ 4 ）： 962 - 973 . doi: 10.1021/acs.accounts.0c00060 http://dx.doi.org/10.1021/acs.accounts.0c00060 Molecular packing： another key point for the performance of organic and polymeric optoelectronic materials LIU Y C ， LI C S ， REN Z J ， et al . All-organic thermally activated delayed fluorescence materials for organic light-emitting diodes ［J］. Nat. Rev. Mater. ， 2018 ， 3 （ 4 ）： 18020-1-20 . doi: 10.1038/natrevmats.2018.20 http://dx.doi.org/10.1038/natrevmats.2018.20 All-organic thermally activated delayed fluorescence materials for organic light-emitting diodes XU S ， CHEN R F ， ZHENG C ， et al . Excited state modulation for organic afterglow： materials and applications ［J］. Adv. 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ChemRxiv ， 2020 ， doi： 10.26434/chemrxiv.12727649.v1 http://dx.doi.org/10.26434/chemrxiv.12727649.v1 . Thermally activated delayed fluorescence from locally excited state： theoretical prediction and experimental validation SCHLEPER A L ， GOUSHI K ， BANNWARTH C ， et al . Hot exciplexes in U-shaped TADF molecules with emission from locally excited states ［J］. Nat. Commun. ， 2021 ， 12 （ 1 ）： 6179-1-9 . doi: 10.1038/s41467-021-26439-w http://dx.doi.org/10.1038/s41467-021-26439-w Hot exciplexes in U-shaped TADF molecules with emission from locally excited states 感谢以下合作者的贡献：王寓、肖小小、欧琪、林诗韵、张天、耿华、廖奕和帅志刚等。本文专家审稿意见及作者回复内容的下载地址： http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20220319. http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20220319. 10.37188/CJL.20220319 O482.31 A 1000-7032（2023）01-0115-14 刘美惠,彭谦.OLED发光材料的理论计算与分子设计[J].发光学报,2023,44(01):115-128. 刘美惠,彭谦.OLED发光材料的理论计算与分子设计[J].发光学报,2023,44(01):115-128. LIU Meihui,PENG Qian.Theoretical Calculation and Molecular Design of Light-emitting Materials for OLED[J].Chinese Journal of Luminescence,2023,44(01):115-128. LIU Meihui,PENG Qian.Theoretical Calculation and Molecular Design of Light-emitting Materials for OLED[J].Chinese Journal of Luminescence,2023,44(01):115-128. 国家自然科学基金（21973099，22273105）；中央高校基本科研业务费专项资金 Supported by National Natural Science Foundation of China（21973099，22273105）； The Fundamental Research Funds for The Central Universities 2022-09-04 2022-09-25 2023-01-05 2023-02-16 发光学报 1 44

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