分子堆积——影响固态有机小分子力响应发光行为的关键因素

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "分子堆积——影响固态有机小分子力响应发光行为的关键因素" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Molecular Stacking—Key Factor in Mechanical-responsive Luminescent Behaviors of Solid Organic Small Molecules" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "李", "givenname": "爱森", "prefix": "" }, { "lang": "en", "surname": "LI", "givenname": "Ai-sen", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "李爱森(1993－)，女，河北辛集人，博士，天津大学在站博士后，2020年于吉林大学获得博士学位，主要从事力刺激响应材料的相关研究。E-mail: liaisen@tju.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348547&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348543&type=", "big": 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"zh", "text": "李振(1976－)，男，湖北孝感人，博士，教授，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)。2002年于武汉大学化学学院获得理学博士学位；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15 000 余次，H指数71。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，Journal of Physics Materials，Aggregate等国内外期刊编委。", "data": [ { "name": "text", "data": "李振(1976－)，男，湖北孝感人，博士，教授，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)。2002年于武汉大学化学学院获得理学博士学位；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15 000 余次，H指数71。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，Journal of Physics Materials，Aggregate等国内外期刊编委。" } ] }, { "rid": "cor2", "lang": "en", "text": "E-mail: lizhentju@tju.edu.cn", "data": [ { "name": "text", "data": "E-mail: lizhentju@tju.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "李振(1976－)，男，湖北孝感人，博士，教授，2002年于武汉大学获得博士学位，主要从事二阶非线性光学、有机室温磷光、力致发光、聚集诱导发光、传感器、太阳能电池、磁性纳米材料等的研究。E-mail: lizhentju@tju.edu.cn" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348560&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348555&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348560&type=" } ], "data": [ [ { "name": "text", "data": "李振" }, { "name": "text", "data": "(1976－)，男，湖北孝感人，博士，教授，2002年于武汉大学获得博士学位，主要从事二阶非线性光学、有机室温磷光、力致发光、聚集诱导发光、传感器、太阳能电池、磁性纳米材料等的研究。E-mail: " }, { "name": "text", "data": "lizhentju@tju.edu.cn" } ] ] } ], "email": "lizhentju@tju.edu.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "label": "1", "text": "天津大学-新加坡国立大学福州联合学院 天津大学福州国际校区， 福建 福州 　 350207;", "data": [ { "name": "text", "data": "天津大学-新加坡国立大学福州联合学院 天津大学福州国际校区， 福建 福州 　 350207;" } ] }, { "lang": "en", "label": "1", "text": "Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China;", "data": [ { "name": "text", "data": "Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China;" } ] } ] }, { "id": "aff2", "intro": [ { "lang": "zh", "label": "2", "text": "天津大学 分子聚集态科学研究院， 天津 　 300072；", "data": [ { "name": "text", "data": "天津大学 分子聚集态科学研究院， 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;" } ] } ] }, { "id": "aff3", "intro": [ { "lang": "zh", "label": "3", "text": "武汉大学 化学与分子科学学院， 湖北 武汉 　 430072", "data": [ { "name": "text", "data": "武汉大学 化学与分子科学学院， 湖北 武汉 　 430072" } ] }, { "lang": "en", "label": "3", "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" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "力刺激响应型有机发光小分子因其独特的发光性质在信息加密、光学存储、压力传感器等领域具有潜在应用，引起了广泛关注。其相关发光特性并不只来源于单分子结构，更与分子聚集态不同的堆积模式密切相关，因此，如何调控分子堆积模式是获得功能化发光材料的关键。本文主要从力致变色和力致发光材料体系出发，概述了几种调控分子间相互作用的策略，突出强调了分子堆积与发光性能之间的关系，为研究具有新颖发光特性的发光材料提供了研究思路，希望促进有机发光材料的进一步发展。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Mechanical-responsive organic luminogens have potential applications in the fields of information encryption, optical storage, pressure sensors, " }, { "name": "italic", "data": [ { "name": "text", "data": "etc" } ] }, { "name": "text", "data": ". due to their unique luminescent properties, and have attracted widespread attention. Their luminescent properties are not only derived from the single-molecule structure, but also closely related to the different stacking modes of molecular aggregates. Therefore, how to control the molecular stacking mode becomes a key issue for obtaining functional luminescent materials. This review mainly focuses on the material system of mechanochromism and mechanoluminescence, outlines several strategies to regulate the intermolecular interactions, and highlights the relationship between molecular stacking and luminescent performance, which paves a new way to design novel luminescence materials and further promotes the development of organic luminescent materials." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "外力" } ], [ { "name": "text", "data": "力致变色" } ], [ { "name": "text", "data": "力致发光" } ], [ { "name": "text", "data": "分子堆积" } ], [ { "name": "text", "data": "分子间相互作用" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "external force" } ], [ { "name": "text", "data": "mechanochromism" } ], [ { "name": "text", "data": "mechanoluminescence" } ], [ { "name": "text", "data": "molecular stacking" } ], [ { "name": "text", "data": "intermolecular interactions" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "有机发光小分子可通过分子间非共价键相互作用形成分子聚集体。目前，分子聚集体主要以π-π堆积、氢键、卤素键等分子间相互作用作为重要的组装驱动力，呈现H-聚集、J-聚集、交叉偶极堆积(X-聚集)等堆积模式。有机发光小分子在聚集态时的发光性能与单分子态并不完全相同，充分说明有机固体的发光性能很大程度与分子聚集态结构相关，而不仅仅由分子结构决定" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } } ], "rid": [ "R1", "R2", "R3", "R4" ], "text": "1-4", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。通过修饰分子结构及细微调整官能团，可诱导形成不同的分子聚集态堆积结构，从而调控发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } } ], "rid": [ "R5", "R6", "R7" ], "text": "5-7", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同一分子结构也可呈现多晶相排列，实现材料发光性能的调控" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。为了更为方便直观地反映分子堆积对材料性质的影响，基于分子堆积的环境敏感特性，人们通过控制温度、力、溶剂极性、溶液浓度等因素调控分子堆积实现了材料的不同发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，力刺激响应型材料引起了广大科研工作者的极大研究兴趣，这也是近些年来新兴的研究领域之一。力是一种常见的刺激手段和能量输入方式。目前，力刺激响应型有机发光小分子的研究主要集中于力致变色材料和力致发光材料(见" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": ")。力致变色材料主要针对材料光致发光的特性，指在外力作用下，材料光物理性质发生明显变化的一类材料，当撤掉外力或通过加热、溶剂熏蒸等方式处理之后，材料的光物理性质又可逆恢复到初始状态。常见应用于力致变色材料研究的力刺激形式主要包括两种：机械研磨力和静压力。外力作用可以改变分子堆积模式，从而实现了发光性能的转变，也为全面认识聚集态分子堆积结构与发光性能之间的关系提供了一条有效途径。力致变色材料在文件防伪加密、压敏元件、信息存储显示、压致传感等领域具有广阔的应用前景。与力致变色不同，力致发光又称摩擦发光，是一种古老而神秘的发光现象，指固体材料在外界机械作用力下破裂或者形变而产生发光的现象，实现机械能向光能的直接转变。已报道的相关研究成果充分证明了其发光性能也与聚集态分子堆积结构密切相关" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } } ], "rid": [ "R10", "R11" ], "text": "10-11", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与传统的光致发光或电致发光材料相比，力致发光材料可以利用日常生活中无处不在的机械能作为激发源，从而有效避免了人工产生光/电激发源的需求，有望作为新一代节能、环保和可持续的发光材料，在照明、显示和智能传感等领域具有潜在应用价值。然而，关于力致变色和力致发光现象的机理迄今为止尚未得到合理系统的认知，仍有很多科学问题亟待解决，这同样也意味着相关领域的发展具有巨大潜力。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "外力作用下的力致变色与力致发光现象示意图" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Schematic illustration of mechanochromism(MC) and mechanoluminescence(ML) under external force" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348565&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348575&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348570&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "本文从力刺激响应型有机发光小分子出发，概述了在外力作用下力致变色和力致发光材料的发光机制，分析讨论了分子聚集态堆积方式与发光性能之间的关系。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　力致变色" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "1957年，Schönberg等发现9-(对-硝基苯基-苯亚甲基)-二苯并吡喃受到研磨之后可以由黄色转变为橘红色，且经过长时间放置和二乙醚蒸汽的熏蒸可逆恢复至初始状态" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，力致变色材料初步登上科研舞台。但是，该类材料因并未得到深入研究而沉寂。2001年，国际纯粹与应用化学联合会正式定义力致变色材料，开启了人类对力致变色材料的研究热潮" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "R13", "data": [ { "name": "text", "data": "13" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1　机械研磨力诱导的力致变色现象" } ], "level": "2", "id": "s2a" } }, { "name": "p", "data": [ { "name": "text", "data": "机械研磨力是普遍应用于力致变色材料研究的力刺激方式。2012年，唐本忠等发现化合物(E)-BPHTATPE呈现明显的力致变色现象" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图2(a)", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2(a)" } ] } }, { "name": "text", "data": "所示。通过简单的研磨可导致其荧光从蓝光转变为绿光发射，红移将近30 nm。经研究表明，研磨后晶体长程有序堆积结构被破坏，初始的晶态相向无定型态的转变是其产生力致变色现象的直接原因。相比于无定型态，分子在晶态时通常具有更扭曲的构象，因此研磨后的无定型态粉末发光一般呈现红移趋势。同时，可通过加热的方式实现力致变色过程的可逆调控。随后，他们将该智能变色材料成功应用于可逆书写过程，展现了其潜在的实际应用价值。2015年，吉林大学田文晶和徐斌等报道了具有显著力致荧光增强(off-on)现象和可调谐发光性能的四苯乙烯衍生物AD-TPE" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图2(b)", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2(b)" } ] } }, { "name": "text", "data": "所示。研磨后，分子由稳定的长程有序晶相转变为亚稳态的无定型相。晶态时，TPE与AD之间几乎正交的构象使电子分布完全分离，有效抑制了分子内电荷转移(ICT)过程，导致AD-TPE晶相呈现局域态发光。受到外力扰动时，扭曲的构象被影响，导致给体与受体之间的前线轨道发生重叠，形成ICT态，从而显著提高了发光效率，调节了发射光颜色。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "(a)(E)-BPHTATPE的分子结构式、研磨前后荧光照片、荧光光谱以及XRD图谱" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；(b)AD-TPE的分子结构式、研磨前后荧光照片、荧光光谱以及XRD图谱" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "Molecular structure and the fluorescence photo, spectra and XRD before and after grinding of (E)-BPHTATPE(a) and AD-TPE(b)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } } ], "rid": [ "R14", "R15" ], "text": "14-15", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348579&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348589&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348585&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "李振课题组提出了一种基于空间效应和电子效应调控芘衍生物堆积方式的有效策略，实现了具有力致荧光增强(off-on)性能材料的制备" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "所示。首先，在芘分子两端引入两个叔丁基作为位阻基团，增大分子间距离以使其呈现单分子堆积形式。另外，通过取代基吸电子能力的逐渐增强，使得芘环的电子密度逐渐降低，呈现可调控的紧密堆积结构。其中，PPCHO晶体呈现单分子堆积(424 nm)，发光效率极低(" }, { "name": "italic", "data": [ { "name": "text", "data": "Φ" } ] }, { "name": "text", "data": "＝0.05%)，研磨后，其呈现明亮的蓝绿色发光(461 nm，" }, { "name": "italic", "data": [ { "name": "text", "data": "Φ" } ] }, { "name": "text", "data": "＝ 20.07%)。该现象主要归因于分子由单分子向二聚体堆积模式的转变，且研磨态的二聚体具有较大的重叠轨道和较近的分子距离，呈现无序的堆积模式。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "基于空间和电子效应调控分子堆积的机制以及分子堆积依赖的力致荧光增强分子设计策略" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "]" } ] } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "Mechanism of controlling molecular packing based on the steric and electronic effects and design strategy of molecular packing dependent off-on MC" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "]" } ] } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348595&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348605&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348600&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "基于π-π堆积在晶体发光性质中所扮演的重要角色，吉林大学王悦等设计了力致变色对比分子体系——化合物1和化合物2" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，并分别得到了晶相1a和2a(见" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": ")。有趣的是，研磨之后，两者呈现完全不同的力致变色现象，前者由蓝变绿，后者由绿变蓝，但均为可逆互变过程。经研究发现，" }, { "name": "bold", "data": [ { "name": "text", "data": "1a" } ] }, { "name": "text", "data": "晶体中，分子通过N—H…N强氢键作用形成四聚体螺旋桨结构，有效限制了π-π堆积，而研磨导致晶体趋于无定型态，分子内π-π堆积作用增强，因而呈现力致红移现象。" }, { "name": "bold", "data": [ { "name": "text", "data": "2a" } ] }, { "name": "text", "data": "晶体中，由于亚甲基取代基团的引入使得氢键作用消失和分子柔性增强，π-π堆积成为主要的非共价分子间相互作用。研磨导致蒽环发生滑动形成不平行或分离的结构，削弱π-π相互作用，从而导致发射蓝移。基于分子堆积方式的差异性，机械研磨力作用下材料将呈现不同的变色行为。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "化合物1和2的分子结构式、研磨前后的荧光照片、晶体堆积方式及分子间相互作用分析" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "Chemical structure, fluorescence photos before and after ground, analysis of stacking mode and intermolecular interactions of compound 1 and 2" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348610&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348621&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348617&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　静压力诱导的力致变色现象" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "由于进一步发展力致变色材料的迫切需求，可产生各向同性静压力的金刚石对顶砧装置与诸多光谱技术相结合，逐渐成为研究分子结构与性质之间关系的重要技术手段。2012年，田文晶等以BP2VA为研究对象，提出了分子聚集态结构依赖的力致变色机制" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图5(a)", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5(a)" } ] } }, { "name": "text", "data": "所示。随着压力逐渐增加，BP2VA的分子间π-π相互作用逐渐增强，从而导致其发光由绿光(无π-π作用，J-聚集)转变为橙光(弱π-π作用，H-聚集)，最后转变为红光发射(强π-π作用，二聚体)。分子堆积方式逐渐改变，从而呈现明显的力致变色现象。Yamaguchi等基于对四硫唑噻吩晶体研磨后蓝移和静压力下红移现象的机理分析，充分说明机械研磨和静水压模式分别抑制和增强了三维氢键网络中激基缔合物的形成" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图5(b)、(c)", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5(b)、(c)" } ] } }, { "name": "text", "data": "所示。机械研磨力导致晶体结构被破坏，趋于无定型态，激基缔合物的形成被抑制，从而发光蓝移。而在静压力作用下，分子荧光基团的面对面堆积更为紧密，发光红移。该工作充分证明了两种力刺激形式存在本质差别，前者为各向异性力，后者为各向同性力。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "(a)BP2VA粉末不同聚集态结构下的堆积方式及发射光颜色" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；(b)四硫唑噻吩的分子结构、黄色发光晶体照片及对机械研磨和静压力作用的不同响应行为；(c)四硫唑噻吩晶体的高压荧光光谱及对应荧光照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "(a)Stacking modes and corresponding emission colors for the various molecular aggregation states in BP2VA powder " }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ". (b)Tetrathiazolylthiophene and its yellow-emissive crystals and distinct luminescent responses to mechanical grinding, and hydrostatic pressure. (c)Fluorescence spectra and photos of tetrathiazolylthiophene crystal under high pressure" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348626&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348636&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348631&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "邹勃课题组一直致力于高压下材料结构与发光特性的研究。2014年，他们发现四苯乙烯分子在高压作用下呈现独特的力致变色行为，主要分为三阶段变化" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。初始阶段，压力诱导的分子间相互作用增强，使得激子迁移和非辐射跃迁增强，从而降低发光效率。然而，当压力大于1.44 GPa, C—H…π 和 C—H…C作用增强，有效抑制了芳香环的运动，减少了能量损失，提高了发光效率，表现为明显的压致荧光增强。进一步加压，分子堆积将被破坏趋于无定型态，分子内旋转受限作用被削弱，发光效率降低。他们还发现，由于分子内振动和转动受限，非辐射跃迁能量降低，三苯乙烯晶体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、咔唑晶体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "及1，2，3，4-四苯基-1，3-环戊二烯晶体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "也呈现明显的压致荧光增强现象。基于金刚石对顶砧装置的高压光谱技术在分子聚集态结构与性质的研究中逐渐发挥着不可替代的重要作用，并将有力促进力致变色材料的进一步发展。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "(a)四苯乙烯晶体压力依赖的荧光最强峰位及强度变化趋势；(b)四苯乙烯粉末在5.24 GPa压力范围内的荧光衰减曲线" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "(a)Pressure-dependent fluorescence maximum and intensity of TPE crystals. (b)Typical fluorescence decays of TPE powder for pressures below 5.24 GPa" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348642&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348651&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348646&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　力致发光" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "物质在机械作用(如摩擦、加压、冲击、破碎以及超声等)下产生的发光现象称为力致发光。最早关于该现象的报道来自弗朗西斯·培根于1605年发表的《学术的进展(" }, { "name": "italic", "data": [ { "name": "text", "data": "Advancement of Learning" } ] }, { "name": "text", "data": ")》，其中提到“用刀刮坚硬的糖块时会放出亮光”" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。近年来，池振国教授团队和李振教授团队在力致发光材料领域有很多突出的工作，致力于探究分子堆积结构与发光性能的关系，明确力致发光现象的产生机制" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "R10", "data": [ { "name": "text", "data": "10" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } } ], "rid": [ "R10", "R11" ], "text": "10-11", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　同质多晶力致发光现象的构性研究" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "由于化学微环境的不同，物质可以形成两种或两种以上不同晶体结构的现象被称为同质多晶(Polymorphism)，这是晶体独有的一个特征。相同的分子结构会导致不同的非共价分子间和分子内相互作用，如范德华力、氢键和π-π堆积等，这些相互作用对超分子体系的形成具有重要意义。2016年，李振等报道了一种具有高亮度力致发光特性的四苯乙烯类化合物(TMPE)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。即使在日光及微弱力作用的条件下，也可以观察到清晰可见的明亮蓝色荧光，如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "所示。他们进一步通过缓慢挥发溶剂的方法，得到了两种截然不同的晶体。其中，点群为" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": "2" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "(" }, { "name": "italic", "data": [ { "name": "text", "data": "c" } ] }, { "name": "text", "data": ")的块状晶体(Cp-form)具有力致发光性质，而点群为" }, { "name": "italic", "data": [ { "name": "text", "data": "C" } ] }, { "name": "text", "data": "2的针状晶体(Cc-form)则没有力致发光性质，分子堆积结构的不同导致了分子间作用力(C—H…π和C—H…O)的巨大差异。经晶体结构解析可得，块状晶体拥有更多且更强的分子间相互作用力，有效限制了分子的振动、转动和滑动，进而导致外力带来的能量难以通过分子的运动耗散，从而发出荧光。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "(a)具有力致发光性能的Cp-form晶体堆积方式；(b)Cp-form晶体日光及紫外光下的照片；(c)Cc-form晶体日光及紫外光下的照片；(d)无力致发光性能的Cc-form晶体堆积方式；(e)TMPE不同晶相的荧光和力致发光光谱；(f)TMPE的日光及黑暗条件的力致发光照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "(a)Stacking mode of the ML-active Cp-form crystal. Images of the Cp-form crystal(b) and Cc-form crystal(c) under daylight and under UV light. (d)Stacking mode of the ML-inactive Cc-form crystal. (e)Fluorescence and ML spectra of TMPE in different phases. (f)ML images of the as-prepared TMPE sample upon grinding under daylight and in the dark" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348656&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348662&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348659&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "之后，李振课题组又发现了一种具有同质多晶力致发光现象的三苯胺衍生物(TPA-" }, { "name": "italic", "data": [ { "name": "text", "data": "o" } ] }, { "name": "text", "data": "-3COOMe)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，见" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "。其中，扭曲分子结构可以有效避免分子聚集状态下的π-π堆积，有利于力致发光效应。同时，3个酯基的引入可以有效促进三线态，产生磷光。该工作成功制备了两种具有明显不同发光性能的多晶相。晶相A具有明显室温磷光特性，但没有力致发光现象。其为" }, { "name": "italic", "data": [ { "name": "text", "data": "Pī" } ] }, { "name": "text", "data": "点群的中心对称体系呈现紧密的反向平行层状堆积方式，每个分子处于均一的化学环境中，拥有多重分子间相互作用(C—H…O和C—H…π)，可以有效限制分子内运动，减少非辐射跃迁能量损失，促进室温磷光的产生。相比于晶体A，晶体B的点群为" }, { "name": "italic", "data": [ { "name": "text", "data": "Pn" } ] }, { "name": "text", "data": "，属于非中心对称结构，分子堆积较为松散，分子间作用力较弱，填充式的堆积结构可在一定程度限制力作用下分子的滑移，非辐射跃迁能量损失大幅度降低；而且由于晶体B堆积结构缺少对称中心，破裂表面的电荷积累导致了更强烈的电子轰击，因此晶体B力致发光现象显著却无磷光发射。该工作充分证明分子堆积对于材料的功能化具有重要的决定性作用。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "(a)TPA-" }, { "name": "italic", "data": [ { "name": "text", "data": "o" } ] }, { "name": "text", "data": "-3COOMe多晶相的不同发射形式和性能；(b)晶体A的堆积方式；(c)晶体B的堆积方式" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "(a)Different emission forms and performance of compound TPA-" }, { "name": "italic", "data": [ { "name": "text", "data": "o" } ] }, { "name": "text", "data": "-3COOMe in polymorphs. The packing modes of crystal A(b) and crystal B(c)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348665&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348670&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348666&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2018年，中山大学池振国等报道了一种基于同一分子结构的可调控力致发光的分子CDpP。他们成功获得了具有不同堆积方式的两种晶体CDpP-B和CDpP-G，在室温条件、外力刺激下分别发射出蓝光和绿光" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "所示。飞秒瞬态荧光光谱数据表明，该差异主要来源于激发态辐射跃迁路径不同。晶体CDpP-B中存在更多的C—H…π作用，使分子中二苯胺基团上的苯环旋转受限，抑制了激发态弛豫时的构象转变，使其表现为局域态蓝光发射；相反，晶体CDpP-G中存在较少的C—H…π作用，激发态时二苯胺部分可发生自由旋转，使其表现为分子内扭曲电荷转移的绿光发射。通过该项研究，他们提出了通过分子间相互作用(C—H…π)调控力致发光过程中激发态性质，进而改变力致发光的颜色，充分体现了分子间作用力在材料功能化过程中的重要性。" } ] }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "(a)CDpP-B和CDpP-G晶型的单晶结构和荧光照片；(b)CDpP-B(上)和CDpP-G(下)晶相的荧光光谱和力致发光光谱；(c)CDpP-B(上)和CDpP-G(下)晶型的力致发光照片，“B”和“G”分别代表蓝色和绿色固体荧光" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.9" } ], "title": [ { "name": "text", "data": "(a)Single crystal structures and luminescence pictures of CDpP-B and CDpP-G. (b)Fluorescence spectra/ML spectra of CDpP-B(above) and CDpP-G(below). (c)Photographs showing: blue and green solid-state fluorescence(top right) with letters “B” and “G” and the generation of ML(the light spot) for CDpP-B(above) and CDpP-G(below)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348674&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348678&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348675&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　分子结构微调力致发光现象的构性研究" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "另一方面，通过修饰分子结构、微调分子堆积排列方式，也可有效实现力致发光性能的调控。2016年，池振国等将具有聚集诱导发光特性的四苯乙烯单元与甲酰基相结合，制备了具有明显力致发光特性的AIE-ML(" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A)" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "所示，甲酰基取代的" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Ac和限制苯环运动的" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-FP" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "A均无明显力致发光现象。经单晶分析可知，" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A为单斜晶系非中心对称点群" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": "2" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "，两分子之间通过两种不同的C—H…O氢键作用，形成链状堆积结构。相比之下，" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Ac和" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-FP" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "A晶体中，分子以平行或反平行排列形成二聚体结构，有效地使晶体结构对称性增加，形成中心对称非极性空间群。该项工作充分证明，四苯乙烯和甲酰基单元之间的协同作用是形成非中心对称晶体结构和净偶极矩的关键因素，可以有效地促进晶体破裂表面压电性质，触发独特的力致发光现象。" } ] }, { "name": "fig", "data": { "id": "F10", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图10" } ], "title": [ { "name": "text", "data": "(a)目标化合物分子结构；(b)" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Ac、" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A 和 " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-FP" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "A的力致发光光谱以及" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A的力致发光照片；(c)" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Ac、" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A和" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-FP" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "A的分子堆积和分子间相互作用分析" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.10" } ], "title": [ { "name": "text", "data": "(a)Molecular structures of the target compounds. (b)ML spectra of " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Ac, " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A and " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-FP" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "A, ML images of " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A. (c)Molecular packing and intermolecular interactions in single crystals of " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "Ac, " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-P" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "A and " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-FP" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "A" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348681&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348685&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348683&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "李振等将聚集诱导发光与自组装单元相结合，成功制备了噻吩取代的纯有机力致发光分子tPE-2-Th和tPE-3-Th，即使在日光下也呈现明亮的力致发光现象" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "29", "type": "bibr", "rid": "R29", "data": [ { "name": "text", "data": "29" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，见" }, { "name": "xref", "data": { "text": "图11(a)", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11(a)" } ] } }, { "name": "text", "data": "。如" }, { "name": "xref", "data": { "text": "图11(b)", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11(b)" } ] } }, { "name": "text", "data": "所示，扭曲的分子结构使得晶体内部均不存在π-π相互作用或H/J-聚集。苯环取代的tPE-Ph晶体中分子呈现反平行堆积的中心对称结构，无力致发光特性。噻吩环取代的tPE-2-Th和tPE-3-Th晶体中的分子同方向紧密平行堆积，整个晶体以鱼骨结构层层堆积，形成了具有力致发光特性的非中心对称晶体。而且，受到力刺激之后，非中心对称晶体的较大偶极矩有利于阳离子和阴离子的高效复合，促进力致发光效应。另外，该项研究基于tPE-2-Th分子成功建立了压力与力致发光强度之间的线性关系，并应用于灵活且可穿戴的力致发光设备，展现了其在通信、信息存储和医疗保健中的潜在应用。" } ] }, { "name": "fig", "data": { "id": "F11", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图11" } ], "title": [ { "name": "text", "data": "(a)纯有机力致发光材料的分子设计及其在灵活且可穿戴的力致发光设备的应用；(b)tPE-2-Th、tPE-3-Th和tPE-Ph的单晶结构、堆积模式及荧光照片" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "29", "type": "bibr", "rid": "R29", "data": [ { "name": "text", "data": "29" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.11" } ], "title": [ { "name": "text", "data": "(a)Molecular design of novel pure organic ML materials. Some potential applications measured on the basic and wearable ML device(tPE-2-Th). (b)Single-molecular geometries, packing modes and fluorescence photos of tPE-2-Th, tPE-3-Th, and tPE-Ph in crystal" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "29", "type": "bibr", "rid": "R29", "data": [ { "name": "text", "data": "29" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348687&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348689&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348688&type=" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "如上所述，分子的电子组态可以显著影响分子堆积，同时，分子堆积越为紧密，越能够有效限制分子机械运动，减少外力刺激下非辐射跃迁的能量损失，从而促进材料固态时的力致发光性能。李振课题组将卤素原子(F，Cl，Br)引入无力致发光性能的TPA-CHO，成功制备了3个具有显著力致发光性能的三苯胺衍生物" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图12(a)", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12(a)" } ] } }, { "name": "text", "data": "所示。卤原子的引入改变了分子的电子结构，从而使得分子堆积方式发生改变，见" }, { "name": "xref", "data": { "text": "图12(b)", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12(b)" } ] } }, { "name": "text", "data": "。晶体状态下，结构较为刚性的分子的堆积排列可有效抑制可能的分子滑移或崩塌；并且卤原子的引入显著增强了分子间相互作用，从而减少外力作用下的非辐射能量损失，促进了力致发光现象的出现。另外，李振课题组还报道了较为罕见的有机力致磷光分子。如" }, { "name": "xref", "data": { "text": "图12(c)", "type": "fig", "rid": "F12", "data": [ { "name": "text", "data": "图12(c)" } ] } }, { "name": "text", "data": "所示，制备了4种溴取代的芴基衍生物，且取代位置的不同也导致了发光性能的差异" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。其中，BrFlu-CBr呈现力致发光光谱的三色转换。在外力刺激下，其表现为青色发光，经过一段时间，转变为蓝色发光。当撤掉外力刺激，可观察到明显的白绿色磷光发射。Br原子的引入通过外源重原子效应，可以有效增强激发单重态和三重态之间的自旋轨道耦合，提高系间蹿越速率常数；并且由于Br…Br分子间作用的存在，BrFlu-CBr的分子结构更为刚性，在引入外力刺激时，三重态的振动损失和分子滑移在很大程度上被抑制。一旦受到研磨，有序晶格将会塌陷并转化为微晶。在该过程中产生的激发态，包括稳定的三重态，可以通过辐射途径返回基态，诱导出现力致荧光和力致磷光。更多相关工作证明，不同的卤原子取代位置的差异可产生不同的力致发光性能，与分子堆积、分子间相互作用紧密相关。" } ] }, { "name": "fig", "data": { "id": "F12", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图12" } ], "title": [ { "name": "text", "data": "(a)TPA-CHO-2" }, { "name": "italic", "data": [ { "name": "text", "data": "X" } ] }, { "name": "text", "data": "衍生物的化学结构和力致发光照片；(b)TPA-CHO与TPA-CHO-2F的晶体结构" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；(c)重原子效应的影响并将其引入芴衍生物体系，BrFlu-CBr外力作用下的多色转换力致发光现象" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.12" } ], "title": [ { "name": "text", "data": "(a)Chemical structure and ML images of TPA-CHO-2" }, { "name": "italic", "data": [ { "name": "text", "data": "X" } ] }, { "name": "text", "data": ". (b)Crystal structure of TPA-CHO and TPA-CHO-2F" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "30", "type": "bibr", "rid": "R30", "data": [ { "name": "text", "data": "30" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ". (c)Influence of the heavy atom effect(HAE), combination of fluorene derivatives with the HAE, and multicolor switching of triboluminescence for BrFlu-CBr upon introduction of a mechanical stimulus" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "R31", "data": [ { "name": "text", "data": "31" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "．" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348690&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348692&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348691&type=" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　力致变色&力致发光" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "如上文所述，力致变色与力致发光现象均与分子堆积方式以及分子间相互作用密切相关。那么，力致变色与力致发光材料之间是否存在某种内在联系呢？2018年，李振团队设计了4个具有平面结构的芘衍生物，性能各异" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "R32", "data": [ { "name": "text", "data": "32" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，如" }, { "name": "xref", "data": { "text": "图13(a)", "type": "fig", "rid": "F13", "data": [ { "name": "text", "data": "图13(a)" } ] } }, { "name": "text", "data": "所示。这4种化合物在稀溶液态具有相似的光学性质，但在固态却显著不同，主要归结于堆积方式的差异。有趣的是，Pyrene既没有力致变色也没有力致发光性能，Py-H仅具有力致变色性能，Py-Br仅具有力致发光性能，而Py-Bpin具有力致变色和力致发光两种性能。Pyrene和Py-Br具有强的二聚体重叠结构、π-π相互作用以及相邻分子之间的激子耦合作用，主要表现为准分子发射，而Py-H和Py-Bpin主要表现为单分子发射。Py-H和Py-Bpin的力致变色性能主要来源于研磨后增强的相邻分子间π-π相互作用和激子耦合程度。进一步分析可知，Py-Bpin和Py-Br呈现非中心对称，存在强分子间相互作用，增强了晶体结构刚性，有效减少了外力作用下分子坍塌所导致的非辐射跃迁能量损失。而且，破坏强分子间相互作用可以提供比弱分子间相互作用更高的激发能，从而引起力致发光效应。李冰石等也报道了四苯乙烯衍生物" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，其既具有力致变色活性，又具有力致发光活性，而其异构体" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "仅具有力致发光活性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。单晶结构和相关实验结果表明，两种特性均与分子间相互作用和分子构象密切相关。它们的单晶中存在丰富的分子间相互作用，赋予这两种异构体以力致发光性质；而超强的分子间相互作用和平面构象则抑制了不同分子堆积模式之间的可逆转变，从而抑制了" }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的力致变色活性。" } ] }, { "name": "fig", "data": { "id": "F13", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图13" } ], "title": [ { "name": "text", "data": "(a)Pyrene、Py-H、Py-Bpin 和Py-Br的力致变色性质和力致发光性能总结" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "R32", "data": [ { "name": "text", "data": "32" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；(b)" }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " 和 " }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的荧光、力致变色、力致发光性能总结" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.13" } ], "title": [ { "name": "text", "data": "(a)Summary of the MC and ML of Pyrene, Py-H, Py-Bpin and Py-Br" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "R32", "data": [ { "name": "text", "data": "32" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": ". (b)Summary of the fluorescence, MC and ML of " }, { "name": "italic", "data": [ { "name": "text", "data": "p" } ] }, { "name": "text", "data": "-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " and " }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "-NH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "R33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348693&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348695&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348694&type=" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "5　结论" } ], "level": "1", "id": "s5" } }, { "name": "p", "data": [ { "name": "text", "data": "综上所述，分子堆积方式和分子间相互作用在材料的力刺激响应特性中扮演着十分重要的角色。通过施加外力、调控分子堆积方式的有序或无序的改变，从而触发力致变色和力致发光现象，如" }, { "name": "xref", "data": { "text": "图14", "type": "fig", "rid": "F14", "data": [ { "name": "text", "data": "图14" } ] } }, { "name": "text", "data": "所示。力致变色与力致发光虽然均为力刺激响应行为，但发光驱动源完全不同。前者受外力作用，分子堆积发生变化，光致发光光谱产生明显改变，导致变色现象；后者为受到力刺激，晶体破裂的瞬间，电子从基态跃迁至高能态，进而跃进回基态辐射能量得到力致发光光谱，一般较弱。目前，针对力致变色材料的研究主要借助于各向异性的机械研磨力和各向同性的静压力，可诱导分子由晶态转为无定型态、分子堆积更为紧密或是发生相变，从而实现丰富多彩的发光变化，也为深入了解分子聚集态结构与性能的关系提供了新的思路。针对力致发光材料的研究由来已久，普遍认为力致发光现象主要来源于晶体破裂时表面压电效应的产生，同时通过对分子多晶相和结构修饰的研究，进一步说明了越为丰富的分子间相互作用，越是可以有效抑制非辐射跃迁，减少能量损失，从而产生力致发光现象。但是，目前，由于仪器技术方面的限制，对于同步监测和精准分析外力作用下的分子堆积结构变化仍是一个挑战。因此，对力刺激响应行为的内源性机制以及分子堆积与性能之间的关系缺乏深入的理解，限制了力刺激响应型材料进一步发展，这也是该领域发展的机遇。" } ] }, { "name": "fig", "data": { "id": "F14", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图14" } ], "title": [ { "name": "text", "data": "外力作用下分子堆积方式以及力致变色、力致发光性能之间的总结示意图。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.14" } ], "title": [ { "name": "text", "data": "Summary of the relationship of stacking mode, MC and ML under external force." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348696&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348698&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=21348697&type=" } ] } } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献：" } ], "data": [ { "id": "R1", "label": "[1]", "citation": [ { "lang": "zh", "text": [ { "name": "text", "data": "YANG J" }, { "name": "text", "data": ", " }, { "name": "text", "data": "ZHEN X" }, { "name": "text", "data": ", " }, { "name": "text", "data": "WANG B" }, { "name": "text", "data": ", " }, { "name": "text", "data": "et al" }, { "name": "text", "data": ". 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