d8/d10金属有机发色团敏化稀土发光研究

Aiming at achieving rare earth luminescence and imaging application, this project focuses on the design and synthesis of transition metal and lanthanide heteronuclear complexes of multifunctional organic ligands to attain visible to near infrared luminescence of rare earth with high efficiency using metal-organic chromophores as sensitizers through d-f energy transfer. The coordination structures will be most optimized to achieve the best luminescence efficiency of rare earth. The rate of d-f energy transfer and sensitizating efficiency will be modulated through modifying metal-organic chromophores and bridging organic ligands. The mechanism of d-f energy transfer will be explored, and the structure-activity relationship between molecular structures and luminescence properties will be elucidated. The application of transition metal and rare earth complexes in fluorescence imaging and magnetic resonance imaging will be investigated so as to develop responsive imaging agents as well as dual modal fluorescent imaging and magnetic resonance imaging agents.

以稀土发光和成像应用为目标，本项目利用多功能有机配体设计合成过渡金属-稀土异核配合物，借助于金属有机发色团通过d-f能量传递敏化高效率稀土可见-近红外发光。优化配位结构，获得最佳稀土发光效率；改变金属发色团及有机桥联配体，调控d-f能量传递速率和敏化效率；探讨d-f能量传递机理，阐明分子结构与发光性能的构效关系；开展过渡金属-稀土配合物在荧光成像和磁共振成像中的应用，发展响应型成像剂，以及荧光成像和磁共振成像双模式造影剂。

以稀土发光（光致发光、电致发光）性能和成像（荧光成像、磁共振成像）功能为研究目标，围绕多官能团有机配体的设计与稀土分子结构组装、发光器件制备与稀土发光调控、响应型稀土荧光成像和磁共振成像剂构建等问题开展工作，主要取得二方面研究结果。..（i）利用双功能团有机物作为共轭桥联配体设计合成了一系列过渡金属-镧系金属有机化合物；利用高效d-f能量传递成功地获得了高效率稀土发光或双重发射（量子产率30-60%）；利用溶液旋涂法制备三层有机发光二极管，获得了基于稀土发光的、高效率的红光、橙光及白光发射器件，电致发光效率突破文献报道值。..（ii）设计合成了对Fe(II)具有高灵敏响应的Gd(III)配合物磁共振成像和荧光成像双功能探针。配合物能够无损伤地进入细胞并在细胞质内表现出较强的荧光发射，当Fe2+通过2, 2'-联吡啶基团配位时，造影剂的弛豫效率增加了32%，荧光发射几乎猝灭。..项目执行期间，发表标注论文25篇，获得稀土成像授权专利2项，培养出站博士后2名、毕业博士1名、毕业硕士1名。