具有室温磷光发射的非晶态纯有机功能体系的构建及性能

Room temperature phosphorescence (RTP) materials can be applied to the fields of biological imaging, optical recording, anti-counterfeiting system and long-lived OLED material, and so forth. Pure-organic RTP materials are provided with such advantages as low-toxic preparation process, low-cost, easy processing, and so forth. So far, it is still a challenge to develop and enrich the pure-organic RTP material systems. Particularly, constructing the amorphous RTP systems can overcome such disadvantages as complicated preparation process and poor repeatability of crystalline pure organic RTP materials. This proposal aims to further and in-depth research of previous RTP-related results. Choose and synthesize proper dyes (for example, containing bromo substituted moieties) as phosphor molecules. Develop novel functional amorphous RTP supramolecules via macrocyclic host molecule inclusion, induction and host-guest interactions. Construct amorphous supramolecular polymers with RTP emission. Employ the polymerization (or copolymerization) strategy to prepare pure-organic amorphous polymeric materials with RTP emission. Adjust the RTP emission properties of the copolymers via controlling the different ratios between the polymeric monomers and regulating the interactions between the different phosphor polymeric monomers in the system. Introducing the conjugated units with intramolecular charge transfer effect to construct amorphous heavy atom-free pure organic systems with RTP emission. Develop novel pure-organic supramolecular systems and polymers with long emission wavelength range, high RTP emission efficiency and long lifetime, to enrich the research areas of organic photo-electro functional materials and supramolecular chemistry.

室温磷光（RTP）材料可应用于生物成像、光学记录与防伪、长余辉有机电致发光等领域。纯有机RTP材料具有合成过程低毒，成本低廉和易加工等优点。目前为止，发展和丰富纯有机RTP体系仍然是一个挑战。特别的，构建非晶态纯有机RTP体系可以克服晶态材料制备过程复杂，重复性欠缺等缺点。本项目拟在前期工作的基础上，筛选合成合适的共轭分子（如含重原子溴取代单元）作为磷光体，（一）采用超分子主体大环诱导策略，来发展功能新颖的非晶态纯有机RTP超分子和超分子聚合物；（二）采用聚合（或共聚）策略，方便地制备具有RTP功能的纯有机无定形聚合物，通过调控共聚比例和多个不同磷光体单元间的相互作用等来调控其RTP性能。（三）引入含有分子内电荷转移效应的共轭单元，尝试构建非晶态无重原子的纯有机RTP体系。发展RTP发射波长范围更广、高发射效率和长寿命的纯有机超分子和聚合物，丰富有机光电功能材料和超分子化学领域的研究。

本项目旨在发展发射波长范围更广、高发射效率和长寿命的纯有机室温磷光（RTP）超分子和聚合物，丰富有机光电功能材料和超分子化学领域的研究。项目按照计划书执行，完成了项目任务，并取得了超过项目预期目标的系列重要研究成果：构建了水相可见光激发的有机RTP体系，制备了系列RTP发射的共聚物和掺杂聚合物材料体系，RTP发射波长和效率都有明显的提升；发展了单组分且具有多级刺激响应性的高效有机RTP材料、波长可达819nm的近红外有机RTP体系、流体态的有机RTP体系、基于外部重原子效应策略的有机RTP体系、基于引入微量“三线态陷阱”添加组分作为缺陷促进其引起的电荷再结合的机理、通过能级匹配的双组分掺杂实现高效长余辉室温磷光的新策略、基于TS-FRET机制调控荧光和有机RTP之间能量转移的发光体系等。项目执行期间在Sci Adv，Natl Sci Rev，Nature Commun，JACS，Angew（8篇），CCS Chem（5篇）等国内外主流期刊发表论文53篇，申请发明专利13项，其中10项已授权，2项专利成功实现了转化。获得上海市自然科学二等奖等科研奖励。积极参加国际学术交流与合作，国际合作的研究成果在Chem Soc Rev，Adv Mater，Adv Optical Mater和Chem Sci等期刊发表，新增获得了基金委国际合作重点项目的资助，参加国际学术会议并做邀请报告多次。项目执行期间培养出站博士后1人，博士学位获得者4人，培养硕士学位获得者5人。