纯有机室温磷光材料研究现状与策略 增强出版

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "纯有机室温磷光材料研究现状与策略" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "Research Status and Strategy of Pure Organic Room Temperature Phosphorescent Materials" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "郑", "givenname": "贤", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "ZHENG", "givenname": "Xian", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "郑贤（1997-），女，重庆人，硕士研究生，2019年于重庆理工大学获得学士学位，主要从事聚合物光功能材料的研究。 E-mail： 1150078413@qq.com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862888&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862894&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862891&type=", "width": "25.00000191", "height": "29.99998474", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "郑贤" }, { "name": "text", "data": "（1997-），女，重庆人，硕士研究生，2019年于重庆理工大学获得学士学位，主要从事聚合物光功能材料的研究。 E-mail： " }, { "name": "text", "data": "1150078413@qq.com" } ] ] } ], "email": "1150078413@qq.com", "deceased": false }, { "name": [ { "lang": "zh", "surname": "杨", "givenname": "朝龙", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "YANG", "givenname": "Chao-long", "namestyle": "eastern", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "" } ], "role": [ "corresp", "corresp" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "E-mail： yclzjun@163.com", "data": [ { "name": "text", "data": "E-mail： yclzjun@163.com" } ] }, { "rid": "cor2", "lang": "zh", "text": "Email： yclzjun@163.com", "data": [ { "name": "text", "data": "Email： yclzjun@163.com" } ] } ], "bio": [ { "lang": "zh", "text": [ "杨朝龙（1985-），男，云南马关人，博士，教授，2013年于中国科学院大学获得博士学位，主要从事光功能高分子材料方面的研究。 E-mail： yclzjun@163.com" ], "graphic": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862901&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862911&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862905&type=", "width": "25.00000000", "height": "30.00000000", "fontsize": "" } ], "data": [ [ { "name": "text", "data": "杨朝龙" }, { "name": "text", "data": "（1985-），男，云南马关人，博士，教授，2013年于中国科学院大学获得博士学位，主要从事光功能高分子材料方面的研究。 E-mail： " }, { "name": "text", "data": "yclzjun@163.com" } ] ] } ], "email": "yclzjun@163.com", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "text": "重庆理工大学 材料科学与工程学院， 重庆　400054", "data": [ { "name": "text", "data": "重庆理工大学 材料科学与工程学院， 重庆　400054" } ] }, { "lang": "en", "text": "School of Material Science and Engineering， Chongqing University of Technology， Chongqing 400054， China", "data": [ { "name": "text", "data": "School of Material Science and Engineering， Chongqing University of Technology， Chongqing 400054， China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "纯有机室温磷光材料因其成本低廉和性能易调控等优点，成为目前功能材料领域研究的热点。本文详细介绍了近年来纯有机室温磷光材料的发展，系统归纳了纯有机小分子晶体、聚合物和智能响应的室温磷光材料进展，并总结了在室温大气环境下实现有机室温磷光的有效策略。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Pure organic room temperature phosphorescence materials have become a research hotshots in the field of functional materials because of their low cost and easy regulation of performance. In this work， the development of pure organic room temperature phosphorescence materials in recent years is introduced in detail. The pure organic small molecular crystals， polymers and intelligent room temperature phosphorescence materials were systematically summarized. Finally， the effective strategies of realizing organic phosphorescence in room temperature atmosphere are summarized." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "纯有机材料" } ], [ { "name": "text", "data": "室温磷光（RTP）" } ], [ { "name": "text", "data": "长余辉" } ], [ { "name": "text", "data": "晶体" } ], [ { "name": "text", "data": "聚合物" } ], [ { "name": "text", "data": "智能材料" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "pure organic materials" } ], [ { "name": "text", "data": "room temperature phosphorescence" } ], [ { "name": "text", "data": "afterglow" } ], [ { "name": "text", "data": "crystal" } ], [ { "name": "text", "data": "polymer" } ], [ { "name": "text", "data": "smart materials" } ] ] } ], "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": "长余辉发光是一种独特的光物理现象，是指材料在撤去激发光源后仍然能够持续发光一段时间的现象。长余辉发光也叫超长室温磷光，这种现象一般存在于无机材料中，例如夜明珠。迄今为止，无机长余辉材料的研究已经取得了长足的发展，其发光机理较为成熟，主要有空穴转移、位形坐标和电子传输三种模型" }, { "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": "3", "type": "bibr", "rid": "R3", "data": [ { "name": "text", "data": "3" } ] } } ], "rid": [ "R1", "R2", "R3" ], "text": "1-3", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。国内外研究者已经开发出大量的无机长余辉材料，并在夜光照明、生物成像等领域得到了广泛应用。然而，无机长余辉材料制备过程中所用到的稀土材料较为昂贵以及复杂的合成工艺限制了其进一步发展。相对于无机长余辉材料，有机室温磷光（Room temperature phosphorescence，RTP）材料由于价格低廉、合成简便、生物相容性好、柔性以及官能团易修饰等优点，在生物成像、光学记录、信息存储、防伪系统等诸多高新科技领域有着诱人的应用前景" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } } ], "rid": [ "R4", "R5", "R6", "R7", "R8", "R9" ], "text": "4-9", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "有机磷光材料的发光机理主要是雅布伦斯基定律。物质受到激发后，由单重基态（S" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "）激子吸收能量（主要为光子）跃迁至单重激发态（S" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "），经过内转换弛豫至较为稳定的单重激发态（S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "）。此时激子若以光辐射形式释放到达S" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "则产生荧光（Fluorescence，FL）现象，发光寿命一般在纳秒级别。而当通过系间窜越到三重激发态（T" }, { "name": "sub", "data": [ { "name": "text", "data": "n" } ] }, { "name": "text", "data": "）、内转换到较为稳定的三重激发态（T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "）后，再以光辐射形式释放能量到S" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "时会伴随着磷光（Phosphorescence，PL）现象产生。由于这一过程是禁阻的，因此磷光寿命较长，通常为微秒级或亚毫秒级别以上。热活化延迟荧光（Thermally activated delayed fluorescence，TADF）由于S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "和T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "能量相近，在S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "态和T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "态振动能级间较强的耦合情况下，容易从T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "发生反系间窜越到S" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "后以光辐射形式释放能量到达S" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "，其发光寿命介于荧光和磷光之间。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "有机RTP材料在不含稀土等金属的情况下，可通过结构修饰改善其发光性能。一般来说，有机化合物的长余辉可归为超长磷光，由三重态激子的辐射衰变引起" }, { "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": "。由于受到温度、湿度和氧气的影响，常温大气环境下很难被观察到，通常在低温（77 K）和惰性环境下才能实现长寿命发光。近几年，在室温大气环境下有机RTP材料的寿命已经实现毫秒到秒级别的突破，主要通过以下策略实现" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } } ], "rid": [ "R12", "R13", "R14", "R15", "R16", "R17", "R18" ], "text": "12-18", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：（1）引入杂原子、重卤原子、羰基和磺酰基来促进有机发光团的自旋轨道耦合；（2）采用结晶、主客体掺杂、聚合等方法抑制分子振动引起的非辐射跃迁。基于促进高效长寿命有机RTP发射的这两个原理，研究者通过晶体工程" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } } ], "rid": [ "R19", "R20" ], "text": "19-20", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、主客体掺杂" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } } ], "rid": [ "R21", "R22" ], "text": "21-22", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、构建氢键网络" }, { "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": "、引入刚性聚合物基质中" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } } ], "rid": [ "R24", "R25" ], "text": "24-25", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、聚集诱导" }, { "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": "、碳点" }, { "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": "等策略来实现有机RTP发射。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　有机小分子晶体室温磷光材料" } ], "level": "1", "id": "s2" } }, { "name": "p", "data": [ { "name": "text", "data": "有机小分子磷光材料大多以晶体工程的方法实现高效稳定的RTP发射，这得益于晶体堆积产生的结构刚性，有效避免了外界环境中的氧气、水汽等对三线态激子的猝灭" }, { "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": "。通过有机小分子的研究更容易分析分子间的作用力，探究实现长寿命RTP的方法。" } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1　单晶室温磷光材料" } ], "level": "2", "id": "s2a" } }, { "name": "p", "data": [ { "name": "text", "data": "2007年，Politze教授" }, { "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": "提出卤素键（XB），根据一些共价键合卤素原子的最外层部分存在的正静电势区域解释了RTP的产生，分子中的卤素原子与另一分子中的负位点之间形成了一种非共价相互作用，其相互作用的强度按Cl" }, { "name": "text", "data": "<" }, { "name": "text", "data": "Br" }, { "name": "text", "data": "<" }, { "name": "text", "data": "I 的顺序增加。此外，还提出XB在生物系统和晶体工程中的重要性。2015年，唐本忠院士团队" }, { "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": "提出了分子堆积密集的结晶能完美地保护三重态激子，通过丰富而有效的分子间相互作用，抑制C—H振动等耗散的高能非辐射跃迁，从而显著降低T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "的磷光失活速率和环境相互作用的猝灭速率，进而实现持久RTP。通过合理设计具有供-受体结构的CZBP磷光体，实现了寿命达517.87 ms的超长RTP（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "（a））。特别是CZBP在晶体状态下存在蓝-橙色的荧光-磷光双重发射，产生了白光发射，并提出这种双发射策略可以实现单分子白光发射的可能性。之后他们提出需要一个具有相当比例的（n，π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "）和（π，π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "）杂化构型的激发态" }, { "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": "，调整芳基酚酮中的芳香亚基可以有效地调整三重态激子的能级和轨道特征。在大气环境条件下，实现了一系列寿命长达0.23 s和发光效率高达36.0%的全彩纯有机磷光材料。2016年，南洋理工大学赵彦利教授团队" }, { "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": "合成一类固态二溴苯衍生物，通过调控重原子相互作用，在环境条件下获得毫秒级寿命的纯有机绿色磷光。其中末端有两个溴原子的化合物（PhBr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "C" }, { "name": "sub", "data": [ { "name": "text", "data": "6" } ] }, { "name": "text", "data": "Br" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "/PhBr" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "C" }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "Br" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）具有较高的发光效率，这是因为引入的多个分子间卤素键（C—Br—Br）使有机晶体中分子间重原子相互作用增加（" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "（b）），磷光效率提高到21.9%。利用高温下非辐射跃迁增强原理，以这种有机磷光晶体为模型的探针验证了从20~90 ℃的温度传感可行性。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "（a）在365 nm激发下三种晶体的发光现象；（b）有机晶体中分子间卤素键（C—Br—Br）相互作用提升晶体磷光效率。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "（a）Luminescence of three crystals excited at 365 nm. （b）Enhance the crystal phosphorescence efficiency by inter-molecular halogen bond（C—Br—Br） interaction." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862913&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862923&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862918&type=", "width": "76.65002441", "height": "64.38378906", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "2018年，安众福教授团队" }, { "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": "通过合理的分子设计，在有机晶体中利用H-聚集的设计原则，开发出一系列含有三聚氰胺、咔唑单元的有机磷光晶体材料，三聚氰胺衍生物晶体材料的磷光寿命提高25%，达到788 ms，具有肉眼可见的黄色磷光发射。通过单晶分析和理论计算进一步证实了晶体中的H-聚集能有效增强分子间/分子内相互作用，也增强了整个体系的刚性，从而实现长寿命RTP发射。2019年，李振教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "34", "type": "bibr", "rid": "R34", "data": [ { "name": "text", "data": "34" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "在9,9-二甲基黄蒽核中通过连接不同取代基，调控分子间相互作用和分子构型，获得了不同RTP寿命的有机化合物，进一步揭示了分子结构、分子间相互作用和RTP性能之间的关系。其中，1-氯-2-甲基丙基-2-烷基的空间位阻小，在聚集态中形成较强的分子间相互作用，磷光寿命达到601 ms。2020年，王伟周教授等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "35", "type": "bibr", "rid": "R35", "data": [ { "name": "text", "data": "35" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "概述了卤素键在增强RTP中的重要作用，并简要讨论了未来利用卤素键设计、制备和应用RTP材料的光明前景。相关研究团队根据这些设计原则开发出了一系列具有高量子产率的小分子磷光体。然而，对于2020年之前报道的大多数超长有机磷光材料，在大气环境下其磷光量子效率远低于20%，其低亮度和短寿命也无法满足在实际应用中的需求。2020年，池振国教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "36", "type": "bibr", "rid": "R36", "data": [ { "name": "text", "data": "36" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "提出了一种新型分子内卤素键合方案，将重原子和卤素键同时包含在一个分子内，其中CzS" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Br磷光体分子具有较短的" }, { "name": "italic", "data": [ { "name": "text", "data": "d" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "Br" } ] }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "-" } ] } ] }, { "name": "sub", "data": [ { "name": "text", "data": "o" } ] }, { "name": "text", "data": "分子内卤素键，实现了高达52.10%的单组分磷光效率，日光下激发后也能实现肉眼可见的磷光。同年，唐本忠院士团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "37", "type": "bibr", "rid": "R37", "data": [ { "name": "text", "data": "37" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "设计合成了一系列碳氮化物磷光体，研究发现取代基的变化导致了不同的推拉电子效应，对其RTP有着明显的影响。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　共晶室温磷光材料" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "共晶磷光材料相比单组分有机磷光晶体而言具有一定优势，可以有效克服磷光体聚集引起的自猝灭，而且共晶体的外部重原子效应可以进一步促进体系的系间窜越。有机小分子共晶的磷光特性主要归因于其强大的分子间相互作用（氢/卤素键、离子键，π-π堆积等）。早在2011年， Kim教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "38", "type": "bibr", "rid": "R38", "data": [ { "name": "text", "data": "38" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过设计发色团的结构，同时将易产生三重态的芳香醛分子和含有促进三重态的溴重原子分子制备成共晶，通过将卤素键结合到分子晶体中制备出了磷光颜色为蓝色、绿色、黄色和橙色的纯有机共晶材料。同时，当这种发色团在双卤化物晶体中稀释时，在大气环境下磷光量子产率高达55%。这是首次通过将芳香族羰基和重原子效应结合的协同作用来提高RTP效率的相关工作。2017年，晋卫军等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "39", "type": "bibr", "rid": "R39", "data": [ { "name": "text", "data": "39" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "利用1,4-二碘全氟苯（A1）和三个不同位置氮原子的菲罗啉（B1、B2、 B3）制备了一系列共晶材料（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "）。它们的晶体结构和光物理性质有着明显的不同，这主要是由于共晶体系中卤素键作用使得T" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "向S" }, { "name": "sub", "data": [ { "name": "text", "data": "0" } ] }, { "name": "text", "data": "更高振动能级的跃迁变得容易，进而控制发射波长，形成不同颜色的磷光发射。同时他们也研究了不同的取代基（甲基、苯基和氯基）对RTP的影响，并构建了一系列的共晶磷光体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "40", "type": "bibr", "rid": "R40", "data": [ { "name": "text", "data": "40" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，研究发现它们的磷光可以通过取代基的供电子基团和吸电子基团进行修饰。为了探索共晶中分子平面性对RTP的影响，他们用蝶形非平面杂环分子苯噻嗪制备了A12的共晶" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "41", "type": "bibr", "rid": "R41", "data": [ { "name": "text", "data": "41" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。共晶中供体分子的非平面性导致供体本身发出弱磷光，并具有相对较强的延迟荧光。2017年，日本九州大学Adachi团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "42", "type": "bibr", "rid": "R42", "data": [ { "name": "text", "data": "42" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "利用电荷分离、电荷转移、电荷重组的策略实现了长达1 h以上的余辉发射。2020年，唐本忠院士也利用这一策略获得了超长余辉材料，值得注意的是受无机长余辉的启发，他们引入了有机陷阱的概念，实现了长达7 h的余辉发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "43", "type": "bibr", "rid": "R43", "data": [ { "name": "text", "data": "43" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2021年，黄维院士团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "44", "type": "bibr", "rid": "R44", "data": [ { "name": "text", "data": "44" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "详细研究了有机磷光分子与π共轭分子形成的共晶磷光材料，并提出弱分子间相互作用可以提高RTP性能的策略。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "在365 nm激发下有机小分子共晶的多彩发光现象" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 2" } ], "title": [ { "name": "text", "data": "Colorful luminescence of organic mixed crystals under 365 nm excitation" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862928&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862937&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862932&type=", "width": "108.04882813", "height": "51.55056763", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　聚合物基室温磷光材料" } ], "level": "1", "id": "s3" } }, { "name": "p", "data": [ { "name": "text", "data": "目前，有机室温磷光材料中依然是以小分子室温磷光材料为主，有机小分子一般在晶体状态下易展现出磷光性能，然而晶体材料在应用时存在着加工性能较差、不稳定等问题。聚合物材料合成简便、成本及毒性较低、功能基团易于修饰，且具有柔性、透明、质轻、较强的拉伸性能等诸多优势，因此开发聚合物体基RTP材料已成为光功能材料领域关注的热点。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "有机小分子能够展现RTP性能很重要的原因是由于晶体紧密的内部堆积从而抑制分子的热运动，并减少氧气和水分子对三重态激子的影响。根据这种设计策略，实现聚合物RTP材料的关键在于形成一种致密的刚性环境以限制分子热运动。聚合物具有较大的分子量和长链，分子链之间的缠结和基团之间的相互作用力有望形成高度的刚性环境，从而有助于聚合物磷光的实现。聚合物RTP材料主要分为两种：一种是掺杂型聚合物基RTP材料，将磷光体直接与聚合物基体进行物理共混，主要利用基体材料与磷光分子之间的非共价相互作用（氢键、色散力、静电力等）来抑制体系的非辐射跃迁从而实现材料的磷光发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "45", "type": "bibr", "rid": "R45", "data": [ { "name": "text", "data": "45" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "46", "type": "bibr", "rid": "R46", "data": [ { "name": "text", "data": "46" } ] } } ], "rid": [ "R45", "R46" ], "text": "45-46", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。但与共价相互作用相比这是一种相对较弱的非定向连接，易受到环境中氧气、水汽等因素的影响，并且由于相分离等原因，随着时间的延长会出现磷光组分的迁移导致磷光性能消失。另一种是键合型聚合物基RTP材料，磷光单元可位于聚合物的主链、侧链、终端或交联结构中。除引入发光中心以外，同时还可以通过共聚等方式引入含有杂原子的功能性基团以提供分子间的弱相互作用力，如碳基、氨基、羟基和磺酸基等。由于这类聚合材料中同时含有共价键和非共价键的相互作用，可对体系的非辐射跃迁进一步抑制，从而提高聚合物的室温磷光性能。" } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　掺杂型聚合物基室温磷光材料" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "自2009年Fraser团队报道了基于聚乳酸的双发射材料以来" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "47", "type": "bibr", "rid": "R47", "data": [ { "name": "text", "data": "47" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，聚合基长磷光材料因其长寿命、大的Stokes位移和广泛的应用而引起了各国研究者的极大兴趣。聚甲基丙烯酸甲酯（PMMA）兼具低透氧性能和刚性，以及较好的溶解性，为有机小分子的掺杂提供了良好的操作空间。早在2013年，Baldo等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "48", "type": "bibr", "rid": "R48", "data": [ { "name": "text", "data": "48" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "就成功将半导体分子掺杂到PMMA中制备得到具有荧光和磷光双重发射的薄膜材料，由于PMMA的刚性使得三重态激子的非辐射衰减率变得非常低，从而实现了有效的磷光发射，其寿命可高达208 ms。后续相关的研究工作也证明了PMMA是一种有效的实现RTP的聚合物基体材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "49", "type": "bibr", "rid": "R49", "data": [ { "name": "text", "data": "49" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "51", "type": "bibr", "rid": "R51", "data": [ { "name": "text", "data": "51" } ] } } ], "rid": [ "R49", "R50", "R51" ], "text": "49-51", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同时，相关的研究结果表明，等规PMMA作为基质对磷光性能的促进效果要明显优于间规和无规PMMA基体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "52", "type": "bibr", "rid": "R52", "data": [ { "name": "text", "data": "52" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2016年，张国庆教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "53", "type": "bibr", "rid": "R53", "data": [ { "name": "text", "data": "53" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "将具有分子内电荷转移特征的" }, { "name": "italic", "data": [ { "name": "text", "data": "N" } ] }, { "name": "text", "data": "-取代萘酰亚胺与PMMA共掺杂，在真空条件下制备了高效的RTP薄膜，其磷光寿命最高可达230 ms。2014年，Koch等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "54", "type": "bibr", "rid": "R54", "data": [ { "name": "text", "data": "54" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "报道了一种利用取代基电子结构和强π-π堆叠相互作用诱导单线态裂变来提高磷光效率的新策略，制备了一系列硼化合物PMMA掺杂薄膜，其发射量子效率超过100%。超高的发射量子效率为无金属RTP材料的光电应用铺平了道路。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "相比于PMMA，聚乙烯醇（PVA）作为一种多羟基聚合物，虽然没有PMMA的多溶解性，但它具有良好的氧屏障性能和更强的氢键形成能力，对磷光性能的提升也是非常有效的，近年来已成为RTP材料领域的明星聚合物基体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "55", "type": "bibr", "rid": "R55", "data": [ { "name": "text", "data": "55" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。早在2018年，本课题组就利用多羧基结构的磷光体G与PVA进行掺杂成膜，由于磷光体与PVA之间形成的氢键极大地抑制了体系的非辐射跃迁，发光薄膜实现了0.28 s的磷光寿命。令人惊喜的是，在254 nm紫外光辐照下，由于PVA之间脱水发生交联从而进一步压缩体系的非辐射跃迁，使其磷光寿命和亮度都得到大幅度提升（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（a））" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "56", "type": "bibr", "rid": "R56", "data": [ { "name": "text", "data": "56" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，掺杂薄膜具有0.71 s的超长寿命和11.23%的高量子产率。受到该工作的启发，我们通过芘衍生物与PVA进行掺杂制备了系列磷光薄膜材料，研究结果表明该系列薄膜材料的磷光性能展现了明显的激发依赖特性，也就是不同的激发波长下可实现余辉颜色由蓝到红的精细调控（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（b））" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "57", "type": "bibr", "rid": "R57", "data": [ { "name": "text", "data": "57" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。除PMMA、PVA基体外，相关研究结果证实PEG（聚乙二醇）、PSS（聚（苯乙烯磺酸））、PNIPAM（聚（" }, { "name": "italic", "data": [ { "name": "text", "data": "N" } ] }, { "name": "text", "data": "-异丙基丙烯酰胺））等基体对RTP性能也有较好的促进效应" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "58", "type": "bibr", "rid": "R58", "data": [ { "name": "text", "data": "58" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "（a）G与PVA的化学结构，掺杂薄膜的制备和实现超长RTP机理图；（b）PYM、HPY、PCA、PBA和PVA的分子结构，以及掺杂薄膜在不同激发波长下对应的相应RTP图像。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "（a）Chemical structure of G and PVA， preparation of doped films and the mechanism diagram of realizing ultra-long RTP. （b）The molecular structures of PYM， HPY， PCA， PBA， PVA and the corresponding RTP images of doped films at different excitation wavelengths." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862941&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862951&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862946&type=", "width": "154.69293213", "height": "72.34359741", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "空气中的氧是导致磷光性能降低的罪魁祸首之一，因此用封装的形式隔绝氧气是提升磷光性能的有效手段。2020年，Reineke等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "59", "type": "bibr", "rid": "R59", "data": [ { "name": "text", "data": "59" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "设计了一种新型水溶性双发光发射器件。主要分为两步，首先是在石英片上旋涂一层掺杂有TCATPB的PMMA薄膜，然后用水溶性乙烯醇聚合物在掺杂薄膜上再旋涂一层作为氧屏障（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（a））。CATPB分子具有良好的水溶性和较好的形成氢键能力，最终获得可在大气环境稳定保存1个月以上的磷光器件，基于这种独特性质该系列材料可应用于3D打印。马志勇教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "60", "type": "bibr", "rid": "R60", "data": [ { "name": "text", "data": "60" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "成功合成了咔唑异构体（Bd），并进一步以合成的咔唑（Cz）和Bd制备了具有不同Bd取代数的4个Bd衍生物分子，详细研究了这些分子在不同温度以及分散状态下的发光性能。研究表明，在PMMA基质中，通过Cz衍生物激活Bd衍生物自由基阳离子的生成对实现高量子产率和长寿命的黄色RTP是非常有益的。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "（a）TCATPB分子结构与氧屏障薄膜的发光现象；（b）一系列卤化物取代聚乳酸结构与磷光现象；（c）自由基共聚物的发光现象。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig. 4" } ], "title": [ { "name": "text", "data": "（a）Molecular structure of TCATPB and luminescence phenomenon of oxygen barrier film. （b）Structure and RTP phenomenon of a series of halide substituted polylactic acid. （c）Luminescence of free radical copolymers." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862955&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862967&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862961&type=", "width": "115.39160156", "height": "66.91458130", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　键合型聚合物基室温磷光材料" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "键合型聚合物不仅具有抑制非辐射弛豫的能力，而且能有效避免掺杂型聚合物体系中有机小分子磷光体和聚合物基体之间的相分离问题，因此成为近几年的研究热点" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "61", "type": "bibr", "rid": "R61", "data": [ { "name": "text", "data": "61" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "63", "type": "bibr", "rid": "R63", "data": [ { "name": "text", "data": "63" } ] } } ], "rid": [ "R61", "R62", "R63" ], "text": "61-63", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2015年，Fraser教授" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "64", "type": "bibr", "rid": "R64", "data": [ { "name": "text", "data": "64" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "合成了一系列卤化物取代的聚合物BF" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "dbm（" }, { "name": "italic", "data": [ { "name": "text", "data": "X" } ] }, { "name": "text", "data": "）PLA（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（b）），" }, { "name": "italic", "data": [ { "name": "text", "data": "X" } ] }, { "name": "text", "data": "=H，F，Cl，Br，I），在N" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "环境下实现整体聚合物的绿色磷光发射，寿命超过100 ms，并通过重原子效应有效调节其发射寿命。2017年，田禾院士团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "65", "type": "bibr", "rid": "R65", "data": [ { "name": "text", "data": "65" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "将磷光基团连接到聚合物基质的侧链，以限制三重态激子的热运动和非辐射弛豫过程，从而实现大气环境下的RTP发射。他们以丙烯酰胺和不同的潜在磷光单元通过简单自由基聚合制备得到二元共聚物" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "66", "type": "bibr", "rid": "R66", "data": [ { "name": "text", "data": "66" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。该系列共聚物都显示出高效的RTP性能（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（c）），大气环境温度下磷光量子产率高达11.4%。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "2018年，马骧教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "67", "type": "bibr", "rid": "R67", "data": [ { "name": "text", "data": "67" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "将丙烯酰胺与合成的苯酯类磷光体进行自由基共聚，通过构建氢键网络，抑制三重态激子的快速非辐射跃迁，实现了无重原子体系的非晶态纯有机聚合物室温磷光。在室温大气环境下，所制备的聚合物固体粉末显示出蓝色的磷光发射，磷光寿命达537 ms，磷光量子产率为15.39%。与丙烯酰胺共聚后，聚合物中的羰基官能团有效促进了系间窜越，实现了体系自组装诱导长磷光发射，磷光强度和寿命得到大幅度提高。同年,安众福教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "68", "type": "bibr", "rid": "R68", "data": [ { "name": "text", "data": "68" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过多组分化合物的自由基交联共聚，在大气环境条件下实现了激发波长依赖性的颜色可调多组分共聚物磷光发射，激发波长由254 nm变化到370 nm时，磷光颜色由蓝色逐渐向黄色区域转变，磷光寿命长达1.2 s，磷光量子产率为37.5%。研究结果表明，磷光颜色的可调谐机制主要是源于体系中存在两种不同性质的发光组分。2022年，李振教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "69", "type": "bibr", "rid": "R69", "data": [ { "name": "text", "data": "69" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过芳基硼酸衍生物与PVA之间的氢键设计了B—O共价键交联体系，在这种交联的刚性环境下，聚合物薄膜表现出了超长的RTP性能，磷光寿命长达2.43 s，量子产率为7.51%。此外，在该体系中引入另外两种荧光染料（荧光素和罗丹明B），可以通过三重态到单重态的Förster共振能量转移对其磷光颜色进行调整。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "与共聚物相比，均聚物仅用一种单体进行聚合，有利于深入研究聚合物体系中磷光性能的潜在机制。Tomoki等制备了一种简单的有机非晶态聚合物（聚苯乙烯磺酸）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "70", "type": "bibr", "rid": "R70", "data": [ { "name": "text", "data": "70" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，在空气中具有1.2 s的超长磷光寿命（" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（a）），作者采用密度泛函理论计算对单体模型进行了分析，结果表明单线态和三线态之间的最小能隙在0.26 eV，可以有效促进系间窜越。2019年，陈尔强教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "71", "type": "bibr", "rid": "R71", "data": [ { "name": "text", "data": "71" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "首次实现了来自液晶聚合物体系的RTP发射，这一系列材料只有弱分子间相互作用，没有强分子间相互作用和共价交联（" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（b））。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "（a）SPS六聚体的优化几何形状和在干燥PSS薄膜中的磷光过程示意图； （b）小分子和均聚物的结构与室温磷光现象。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "（a）Schematic diagram of optimized geometry of SPS hexamer and phosphorescence process in dry PSS film. （b）The structure and RTP phenomenon of small molecules and homopolymers." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862971&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862980&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862975&type=", "width": "114.57019043", "height": "79.76547241", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　超分子共组装室温磷光材料" } ], "level": "2", "id": "s3c" } }, { "name": "p", "data": [ { "name": "text", "data": "超分子实现RTP的策略主要是利用超分子共组装与大环宿主化合物（葫芦脲、环糊精等）强结合的协同作用。这种材料可以有效克服加工性和水溶性差等缺陷，从而提高材料在固态或水溶液中的量子效率和磷光寿命。CBs（葫芦脲衍生物）是由甘醛和甲醛聚合得到的刚性大环化合物，它可以与带正电荷的客体进行强结合，同时化合物含有的许多羰基可以形成氢键和卤素键，是提高磷光性能的理想主体化合物" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "72", "type": "bibr", "rid": "R72", "data": [ { "name": "text", "data": "72" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。2020年，刘育教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "73", "type": "bibr", "rid": "R73", "data": [ { "name": "text", "data": "73" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "将季铵盐化合物与丙烯酰胺共聚，利用聚合物和主-客体相互作用的优势，实现了材料磷光性能的逐步提升，聚合物与CBs络合后实现了76%的高磷光量子产率和长达2.81 s的磷光寿命（" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（a））。通过这种超分子组装策略，接下来他们通过合成的CB[8]/HA-BrBP超分子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "74", "type": "bibr", "rid": "R74", "data": [ { "name": "text", "data": "74" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "实现了在水溶液中的近红外磷光发射（" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（b））。同年他们合成了一种具有双发射特性的光致发光超分子干凝胶（" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（c）），通过控制湿度可对材料的荧光和磷光性能进行可逆调控" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "75", "type": "bibr", "rid": "R75", "data": [ { "name": "text", "data": "75" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "（a）超长、高效的磷光协同增强（聚合和络合增强）策略；（b）超分子聚合物在水溶液中的构建；（c）基于环糊精干凝胶的磷光体系和可逆白光发射开关。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "（a）Synergistic enhancement strategy（polymerization and complexation enhancement） for ultra-long and efficient room temperature phosphorescence. （b）Construction of supramolecular polymers in aqueous solution. （c）RTP and reversible white emitting switch based on xerogels of cyclodextrin." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862984&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862994&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862989&type=", "width": "140.72607422", "height": "78.75408936", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　智能刺激型室温磷光材料" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "智能室温磷光材料是指材料的磷光颜色、强度和寿命在光、热、机械力等外部刺激条件下发生动态变化的材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "76", "type": "bibr", "rid": "R76", "data": [ { "name": "text", "data": "76" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。与正常RTP材料相比，具有刺激反应效应的材料由于其良好的可逆性、快速响应和易于控制等特性，具有更大的实际应用潜力。" } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4.1　单组分智能室温磷光材料" } ], "level": "2", "id": "s4a" } }, { "name": "p", "data": [ { "name": "text", "data": "对于单组分RTP材料，其分子结构、堆积以及构象的变化在其相应的刺激响应磷光效应中发挥了重要作用。2017年，李振教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "77", "type": "bibr", "rid": "R77", "data": [ { "name": "text", "data": "77" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "实现了基于单组分有机材料分子结构变化的智能响应磷光效应。如" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "（a）所示，苯基硼酸（PBA-R）衍生物在加热刺激下发生脱水缩合反应，形成了三苯基硼氧苷（tPBA-R）结构，结构的改变引起了分子内电子结构和排列改变，同时分子间氢键也发生改变，从而导致磷光性能在加热后消失；但用水蒸气接触后恢复产生磷光发射，从而实现动态可逆的转变过程。随后，他们开发出光诱导的CS-PhCF" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "晶体" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "78", "type": "bibr", "rid": "R78", "data": [ { "name": "text", "data": "78" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，通过光诱导使分子间π-π堆叠距离更近，获得绿色的磷光发射。2020年，黄维院士团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "79", "type": "bibr", "rid": "R79", "data": [ { "name": "text", "data": "79" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "首次报道了两种具有明显的光激活动态磷光性能的吡啶衍生物（PyCz）（" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "（b）），研究表明产生这种现象的主要原因是由于晶体中分子堆叠的形式会影响非辐射跃迁贡献率。经过光活化后晶体的寿命和强度都有很大提升，更重要的是在黑暗中保存一段时间后磷光性能又恢复初始状态，是一个可重复多次的可逆过程，可用于数据存储，在数据存储领域具有较好的应用前景。2021年，本课题组通过简单的点击化学反应制备了一种对水分子具有智能响应的聚合物室温磷光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "80", "type": "bibr", "rid": "R80", "data": [ { "name": "text", "data": "80" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "（" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "（c）），因水分子介入导致聚合物链松散而实现磷光颜色由蓝色转变为绿色。特定基团对化学物质会产生改变进而影响发光性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "81", "type": "bibr", "rid": "R81", "data": [ { "name": "text", "data": "81" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "82", "type": "bibr", "rid": "R82", "data": [ { "name": "text", "data": "82" } ] } } ], "rid": [ "R81", "R82" ], "text": "81-82", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，分子堆积会被机械作用改变产生磷光发射" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "83", "type": "bibr", "rid": "R83", "data": [ { "name": "text", "data": "83" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "84", "type": "bibr", "rid": "R84", "data": [ { "name": "text", "data": "84" } ] } } ], "rid": [ "R83", "R84" ], "text": "83-84", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，因此也具有智能动态发光现象。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "（a）硼酸衍生物中的刺激响应性磷光发射示意图；（b）在大气环境条件下，不同紫外活化时间材料的磷光现象；（c）287 nm激发下薄膜的水诱导RTP颜色变化。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "（a）Schematic diagram of stimulus responsive RTP in boric acid derivative. （b）RTP phenomenon of phosphors with different UV activation time under environmental conditions. （c）Water-induced RTP color change of film under the excitation wavelength of 287 nm." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35862997&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35863008&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35863001&type=", "width": "95.67147827", "height": "60.41033936", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4.2　多组分智能室温磷光材料" } ], "level": "2", "id": "s4b" } }, { "name": "p", "data": [ { "name": "text", "data": "多组分智能室温磷光材料具有结构多样、性能易于调制等优点，在刺激响应过程中，基质中氧浓度和不同组分间分子间距离的变化是导致其智能化的主要原因。2021年，本课题组采用常见的磷光体与丙烯酸类共聚物进行掺杂、通过紫外光持续照射来控制分子的聚集从而提升材料的磷光性能，磷光寿命提升了14倍，达到828.81 ms" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "85", "type": "bibr", "rid": "R85", "data": [ { "name": "text", "data": "85" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同年，本课题组还开发了系列具有紫外辐照时间、激发波长依赖性、浓度依赖性的多重刺激响应的一系列智能聚合物基磷光薄膜" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "86", "type": "bibr", "rid": "R86", "data": [ { "name": "text", "data": "86" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，通过改变不同的条件可以得到具有不同磷光寿命和磷光颜色的发光材料，极大地丰富了智能磷光材料的潜在应用（" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "）。一般情况下大气环境中的氧以三重态形式存在，会猝灭能产生磷光的三重态激子，通过紫外光持续辐照2 min后，可将三线态氧转化为单线态氧，并与周围环境发生相互作用实现耗氧，成功实现了磷光性能的从无到有" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "87", "type": "bibr", "rid": "R87", "data": [ { "name": "text", "data": "87" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "；在环境下放置一段时间后又可以恢复原始状态，具有可逆的光响应磷光效应。这类材料有望在玻璃裂纹检测上应用" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "88", "type": "bibr", "rid": "R88", "data": [ { "name": "text", "data": "88" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。近年来，李振教授团队成功地开发出多组分的可通过加热/研磨调控磷光性能的发光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "89", "type": "bibr", "rid": "R89", "data": [ { "name": "text", "data": "89" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "90", "type": "bibr", "rid": "R90", "data": [ { "name": "text", "data": "90" } ] } } ], "rid": [ "R89", "R90" ], "text": "89-90", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，在加热和研磨过程中可以缩短供受体之间的距离，从而通过能量转移实现有效的磷光性能。刘育教授团队" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "91", "type": "bibr", "rid": "R91", "data": [ { "name": "text", "data": "91" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过CB[8]和蒽共轭溴苯基吡啶盐之间的主-客体络合构建了一个超分子发光纳米体系，因为蒽基会被光氧化为蒽醌，该体系能够在水介质中实现荧光磷光的有效转换，可以在不同的细胞器中进行双细胞器靶向成像。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "（a）字母CQUT的制备以及发光图片；（b）不同辐照时间、不同激发波长以及关闭紫外灯后不同时间字母的磷光照片。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "（a）Preparation and luminescence picture of the letter ‘CQUT’. （b）Afterglow photographs of the letter at different irradiation time， different excitation wavelength and different time after turning off the ultraviolet lamp." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35863012&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35863019&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=35863016&type=", "width": "94.72895813", "height": "59.93045044", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "5　总结与展望" } ], "level": "1", "id": "s5" } }, { "name": "p", "data": [ { "name": "text", "data": "本文对近年来有机小分子单晶和共晶室温磷光材料，掺杂型、键合型聚合基室温磷光材料，超分子室温磷光材料，以及智能刺激响应型室温磷光材料的相关工作进行了综述。总结出在化合物体系中引入卤素重原子（Cl、Br和I）、杂原子（O、N和S）以及羰基等结构可有效促进系间窜越，提高自旋轨道耦合，从而提升材料的磷光性能。但在室温大气环境下实现高亮度和长寿命的磷光发射依然具有挑战性。有机小分子晶体由于其紧密的分子堆积和分子间的强相互作用力形成的刚性环境以及聚合物和超分子通过非共价键、共价键以及交联等形成的分子间强相互作用力所构成的刚性环境，能够有效抑制分子间的非辐射跃迁以及保护三重态激子不被空气中的氧和水分子所猝灭，从而实现高效的磷光发射。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "随着国内外对纯有机室温磷光材料的研究增多，长寿命、高亮度以及颜色可调控的有机RTP材料已被开发出来，有望在生物成像、防伪、信息加密解密等领域广泛应用。但纯有机RTP材料相比无机室温磷光材料的发展时间还是较短，材料体系相对较少，领域依然存在下列问题：（1）纯有机RTP材料的发光亮度不高、寿命不长，日光下难以观察到余辉颜色，在自然光下应用存在困难；（2）在高温、水、富氧等环境下实现长寿命RTP的研究依然很少，有待深入挖掘；（3）纯有机RTP材料的有效激发光源大都在近紫外波段，发光颜色范围较窄，主要集中于蓝绿光区域，实现红色和白光发射的RTP材料依然有较大挑战。因此希望研究者给予有机室温磷光材料更多的关注和支持。相信通过广大研究者的努力，未来有机室温磷光材料的性能将会得到进一步提升，从而有望在不用电或少用电的“绿色光源”领域实现广泛应用。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文专家审稿意见及作者回复内容的下载地址：" }, { "name": "extlink", "data": { "text": [ { "name": "text", "data": "http：//cjl.lightpublishing.cn/thesisDetails#10.37188/ CJL.20220151." } ], "href": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20220151." } } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "R1", "label": "1", "citation": [ { "lang": "zh", "text": [ { "name": "text", "data": "李亚" }, { "name": "text", "data": ". 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