分子聚集态发光展望:聚散不同性相远集体效应叹观止

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "分子聚集态发光展望:聚散不同性相远集体效应叹观止" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Prospect of Luminogens as Aggregates: Collective Effect of Molecular Aggregation" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "李", "givenname": "振", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "LI", "givenname": "Zhen", "namestyle": "western", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" }, { "rid": "aff2", "text": "2" } ], "role": [ "corresp", "first-author" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "LI Zhen,E-mail:lizhen@whu.edu.cn", "data": [ { "name": "text", "data": "LI Zhen,E-mail:lizhen@whu.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "李振(1976-)，男，湖北孝感人，博士，武汉大学化学与分子科学学院教授，天津大学“讲席教授”，博士研究生导师。2002年于武汉大学获得理学博士学位。国家杰出青年科学基金获得者，“科技部中青年科技创新领军人才计划”入选者，国家“万人计划”入选者，英国皇家化学会会士(Fellow of RSC)。2003—2004年，中国香港科技大学化学系Research Associate；2010年，美国佐治亚理工学院化学与化学生物学系访问学者；2014年1—2月，新加坡国立大学Visiting Professor；2018年2月，澳大利亚弗林德斯大学Honorary Visiting Scholar。研究方向为有机、高分子光电功能材料化学，研究对象主要为有机共轭体系和功能高分子，研究范围涉及二阶非线性光学、有机室温磷光、力致发光、聚集诱导发光、传感器、太阳能电池、磁性纳米材料等。至今已发表SCI论文200余篇，他引13 000余次，H指数67。2007年荣获中国化学会“青年化学奖”，2008年入选教育部新世纪优秀人才支持计划，2011年获得霍英东教育基金会青年教师奖，2013年获得国家自然科学基金委杰出青年基金资助，2017年获得国家自然科学一等奖(排名第四)。目前担任《有机化学》，《化学学报》，Polymer Bulletin，Chinese Journal of Polymer Science，《中国科学：化学》，Materials Chemistry Frontiers，ACS Omega，JPhy Materials等国内外期刊编委。E-mail: lizhen@whu.edu.cn" ], "graphic": [], "data": [ [ { "name": "bold", "data": [ { "name": "text", "data": "李振" } ] }, { "name": "text", "data": "(1976-)，男，湖北孝感人，博士，武汉大学化学与分子科学学院教授，天津大学“讲席教授”，博士研究生导师。2002年于武汉大学获得理学博士学位。国家杰出青年科学基金获得者，“科技部中青年科技创新领军人才计划”入选者，国家“万人计划”入选者，英国皇家化学会会士(Fellow of RSC)。2003—2004年，中国香港科技大学化学系Research Associate；2010年，美国佐治亚理工学院化学与化学生物学系访问学者；2014年1—2月，新加坡国立大学Visiting Professor；2018年2月，澳大利亚弗林德斯大学Honorary Visiting Scholar。研究方向为有机、高分子光电功能材料化学，研究对象主要为有机共轭体系和功能高分子，研究范围涉及二阶非线性光学、有机室温磷光、力致发光、聚集诱导发光、传感器、太阳能电池、磁性纳米材料等。至今已发表SCI论文200余篇，他引13 000余次，H指数67。2007年荣获中国化学会“青年化学奖”，2008年入选教育部新世纪优秀人才支持计划，2011年获得霍英东教育基金会青年教师奖，2013年获得国家自然科学基金委杰出青年基金资助，2017年获得国家自然科学一等奖(排名第四)。目前担任《有机化学》，《化学学报》，" }, { "name": "italic", "data": [ { "name": "text", "data": "Polymer Bulletin，Chinese Journal of Polymer Science" } ] }, { "name": "text", "data": "，《中国科学：化学》，" }, { "name": "italic", "data": [ { "name": "text", "data": "Materials Chemistry Frontiers，ACS Omega，JPhy Materials" } ] }, { "name": "text", "data": "等国内外期刊编委。E-mail: " }, { "name": "text", "data": "lizhen@whu.edu.cn" } ] ] } ], "email": "lizhen@whu.edu.cn", "deceased": false }, { "name": [ { "lang": "zh", "surname": "李", "givenname": "倩倩", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "LI", "givenname": "Qian-qian", "namestyle": "western", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [], "bio": [ { "lang": "zh", "text": [ "李倩倩(1983-)，女，湖北公安人，博士，武汉大学化学与分子科学学院教授，博士研究生导师。2009年于武汉大学获得理学博士学位，经过两年在武汉大学物理学院博士后经历后，2011年11月留校工作。2013年入选武汉大学“珞珈青年学者”。2016—2017年，加州大学洛杉矶分校材料科学与工程学院访问学者。研究对象主要是有机共轭体系，研究范围涉及发光材料、太阳能电池、传感器等领域。至今以第一作者或通讯联系人发表SCI论文50余篇，包括Angew. Chem. Int. Ed.，Acc. Chem. Res.，Adv. Functional Mater.，Adv. Energy Mater.，ACS Nano、ACS Energy Lett.等；他引3 000余次，H指数40。2019年获得湖北省化学化工青年创新奖。E-mail: qianqian-alinda@163.com" ], "graphic": [], "data": [ [ { "name": "bold", "data": [ { "name": "text", "data": "李倩倩" } ] }, { "name": "text", "data": "(1983-)，女，湖北公安人，博士，武汉大学化学与分子科学学院教授，博士研究生导师。2009年于武汉大学获得理学博士学位，经过两年在武汉大学物理学院博士后经历后，2011年11月留校工作。2013年入选武汉大学“珞珈青年学者”。2016—2017年，加州大学洛杉矶分校材料科学与工程学院访问学者。研究对象主要是有机共轭体系，研究范围涉及发光材料、太阳能电池、传感器等领域。至今以第一作者或通讯联系人发表SCI论文50余篇，包括" }, { "name": "italic", "data": [ { "name": "text", "data": "Angew. Chem. Int. Ed.，Acc. Chem. Res.，Adv. Functional Mater.，Adv. Energy Mater.，ACS Nano、ACS Energy Lett." } ] }, { "name": "text", "data": "等；他引3 000余次，H指数40。2019年获得湖北省化学化工青年创新奖。E-mail: " }, { "name": "text", "data": "qianqian-alinda@163.com" } ] ] } ], "email": "qianqian-alinda@163.com", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "label": "1", "text": "武汉大学 化学与分子科学学院, 武汉 湖北 430072", "data": [ { "name": "text", "data": "武汉大学 化学与分子科学学院, 武汉 湖北 430072" } ] }, { "lang": "en", "label": "1", "text": "College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China", "data": [ { "name": "text", "data": "College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China" } ] } ] }, { "id": "aff2", "intro": [ { "lang": "zh", "label": "2", "text": "天津大学 分子聚集态研究院, 天津 300072", "data": [ { "name": "text", "data": "天津大学 分子聚集态研究院, 天津 300072" } ] }, { "lang": "en", "label": "2", "text": "Institute of Molecular Aggregation Science, Tianjin University, Tianjin 300072, China", "data": [ { "name": "text", "data": "Institute of Molecular Aggregation Science, Tianjin University, Tianjin 300072, China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "有机光电功能材料的宏观性质是分子聚集效应的客观体现，本文以力致发光和有机室温磷光为例，探讨了分子聚集态结构的影响因素和精细调控策略，并介绍了\"MUSIC\"的理念，以音乐创作形象化材料设计，强调了分子聚集态科学研究的重要性。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "The properties of organic opto-electronic materials are governed by the whole collective as molecular aggregates. Accordingly, the key factors and the control strategies for the structures of molecular aggregates are reviewed by the investigation of mechanoluminescence and organic room temperature phosphorescence materials. The concept of Molecular Uniting Set Identified Characteristic (MUSIC) was proposed by concerning the similarity in the construction of opto-electronic materials and the symphonic performance as real \"music\", highlighting the key role of molecular aggregates." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "分子聚集态" } ], [ { "name": "text", "data": "力致发光" } ], [ { "name": "text", "data": "有机室温磷光" } ], [ { "name": "text", "data": "有机光电材料" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "molecular aggregates" } ], [ { "name": "text", "data": "mechanoluminescence" } ], [ { "name": "text", "data": "organic room temperature phosphorescence" } ], [ { "name": "text", "data": "organic opto-electronic materials" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "1" } ], "title": [ { "name": "text", "data": "引言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "有机材料是由许多分子构成的聚集体，其性能既与分子自身的构型、电子特性、功能位点等密切相关，又受到聚集态时分子间相互作用、排列方式和界面性质等的影响" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "b1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。科学的发展，目前已经从偏重于单分子研究，逐步迈向分子聚集态科学的研究阶段。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "从单分子到分子聚集体，分子数量的叠加并不简单地意味着物质性能定量的改变，往往体现出量变到质变的飞跃，甚至是新功能的产生。改变聚集态结构、形貌、维数和尺寸从而调控其性能，是化学、物理和材料等学科的重要前沿研究领域。然而，微观结构的复杂性和影响因素的多样性，难以获得较为明确的构性关系，导致分子聚集态的精准调控困难重重，对功能分子的设计和性能优化提出了巨大的挑战。近二十年来，分子聚集态科学越来越受到国内外科学家们的广泛关注，随着对聚集态结构和性能的深入研究，微观分子构筑体系的大门逐渐被打开，带来了对材料体系新的认知和精准的调控策略。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2" } ], "title": [ { "name": "text", "data": "从“1+1≫2”到新功能的产生" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "基于“聚集诱导发光(Aggregation-induced emission, AIE)”现象中分子聚集对发光性质“1+1≫2”的重要作用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "b2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，科学家们对分子聚集态逐步高度关注并开展了广泛研究。有机光电功能分子以不同的聚集形式广泛存在于功能薄膜、纳米颗粒、生物富集体系、结晶态等，其分子排列方式和相互作用强弱的差异对其聚集形貌和光电功能都有至关重要的影响。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "随着对分子聚集态科学的不断深入探索，在提高材料光电性能的同时，还获得了一些单分子无法实现的新性质。如力致发光就是一种依赖分子聚集形式，通过机械力刺激分子的有效激发，实现荧光或磷光发射的现象" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "3", "type": "bibr", "rid": "b3", "data": [ { "name": "text", "data": "3" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其发光的方式和强弱与力刺激过程中分子堆积结构的变化，以及聚集态的光致发光属性密切相关。虽然早在1605年，Francis Bacon就发现了这一有趣的发光现象，但受制于机械力作用下微观分子聚集态变化的复杂性和不确定性，其具体的发光机制依然不明晰。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "最近，我们首先从同质多晶的不同力致发光现象出发，详细探讨了分子堆积模式的差异对力刺激响应的影响，提出了获得力致发光的优势分子排列方式" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "b4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "; 同时，通过各种力致发光体系的开发，初步探讨了分子结构-堆积模式-力致发光的关系，并发现了首例纯有机力致磷光现象" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "b5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "类似聚集态新型发光现象还体现在有机室温磷光领域。基于有机体系自身结构的局限性，室温磷光的获取对分子结构和排列方式提出了更为苛刻的要求和挑战。我们从传统光致室温磷光的角度，通过取代基结构的微小调控，实现了分子排列方式的优化，获得了磷光寿命的有效延长和亮度的提升" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "b6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "b8", "data": [ { "name": "text", "data": "8" } ] } } ], "rid": [ "b6", "b7", "b8" ], "text": "6-8", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。比如，我们可以通过运用不同的吸电子基团调节分子内的电子转移程度，调控聚集态时分子的堆积，从而优化其室温磷光性能。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "进一步，通过引入外界的光调控过程，我们首次发现了光诱导纯有机分子室温磷光的动态响应，通过光照前后原位晶体结构的变化，有效印证了室温磷光对分子构象和聚集形式高度灵敏性的响应" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "b9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。深入探讨力刺激和光刺激对晶态结构的不同影响，以及所产生的发光形式和性质的差异，通过精心的分子设计，还获得了同质多晶对外界刺激的差异性响应，即一种晶型体现出力致发光，而另一种晶型体现出光致室温磷光的特性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "b10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。充分表明分子聚集态行为对其性能的决定性作用。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "这些不同的分子聚集形式所带来的不同发光现象和动态响应过程，为聚集态结构的精细调控提供了有效的策略，也带来了新的智能化应用。特别是力致发光的定量监测" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "b11", "data": [ { "name": "text", "data": "11" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，在通信、信息存储以及医疗监护方面提供了全新的应用可能性。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "3" } ], "title": [ { "name": "text", "data": "分子聚集态的内核和发展" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "分子聚集态所体现的宏观光电效应与内在的微观结构密切相关，包括分子的构型和构象、排列方式和相互作用等，它们之间既相互制约又相互影响，共同实现了整体性能的表达。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "针对力致发光材料而言，从增强发光亮度的角度，鱼骨状或类似互锁结构的分子排列方式可有效防止机械力作用下分子发生层间滑移所带来的能量损失，有利于提高辐射跃迁的比例。在力刺激下晶体破碎过程中，不均一的分子排列方式和相互作用可部分调控其断裂面的形成方式；而分子中多个构象的亚稳态和分子间多种相互作用的存在，则有利于提高力致发光的持久性和可逆性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "有机室温磷光现象的获得则对分子聚集态有着完全不同的需求" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "b12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "b13", "data": [ { "name": "text", "data": "13" } ] } } ], "rid": [ "b12", "b13" ], "text": "12-13", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。基于系间穿越的禁阻性和激发三线态的不稳定性等壁垒，主要通过分子间耦合作用的增强，以及n-π和π-π相互作用比例的调节来缓解，大部分体现出杂环共轭体系面面紧密堆积的优势分子排列。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "这两类新型发光材料体现出单个分子与分子聚集体之间性能的极大差异，促使科学家们更多地关注聚集态中分子的排列和堆积，有望通过进一步的研究，发展调控聚集态分子排列的策略和手段，从而优化材料性能。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "4" } ], "title": [ { "name": "text", "data": "展望" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "分子聚集态的研究是一个庞大的系统工程，从分子本征的结构属性、分子间自组装过程的构筑、聚集态的存在方式，到材料的加工过程和外界环境等，都可以实现对其内部结构和形貌的优化。该方面的深入、系统研究，涉及到化学、物理、材料等多学科的交叉和综合应用，是目前光电功能材料领域急需解决的重要科学问题和挑战。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "有机力致发光和有机室温磷光两种新型发光，是聚集效应所产生的新功能。我们经过前期系统的研究，获得了一些“分子结构-分子排列和相互作用-发光性能间”相互关系，体现出分子聚集体的特征性能，可以用英文短语“Molecular Uniting Set Identified Characteristic”来总结该现象" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "b14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，并缩写为MUSIC。因此，我们也可以从另外一个角度诠释分子聚集态行为：如果将原子当做一个个音符，分子可以认为是一小段旋律，而分子聚集体就是多个旋律组合成的交响乐。我们可以用音乐创作形象化材料设计，强调分子聚集态行为的重要性，有望获得更多有别于单个分子特性的多种新功能，促进分子功能的拓展与创新，充分展现分子聚集态科学的奇妙与憧憬。正是：" } ] }, { "name": "p", "data": [ { "name": "text", "data": "分合天下千古事，子丑寅卯感悟迟。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "聚散不同性相远，集体效应叹观止。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "态姿变幻似无迹，科海浮沉渐入迷。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "学思结合无罔殆，妙趣横生见传奇。" } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "b1", "label": "1", "citation": [ { "lang": "en", "text": [ { "name": "text", "data": "LI Q, LI Z. 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