Development of Novel Functionalized Organic Fluorescent Materials Having Polypyridyl Structure

氨基基的邻位取代产生了高效的荧光2,2 ':6',2"-三吡啶（tpy），其荧光在380 nm左右可见。其中6-氨基tpy具有较大的荧光量子产率（Φ=0.70）。另一方面，4′-氨基tpy的变化非常小（<0.01）。我们成功地开发了高荧光的tpys，并提出了在适当位置引入氨基的重要性。4′-苯基苯基（ptp）也表现出高效的荧光。苯基对位取代表明，氨基和二甲氨基ptp表现出明显的红移荧光。光谱和MO计算的溶剂依赖性表明，强给电子基团的引入使HOMO-1的能级高于HOMO。目前还没有通过控制分子轨道能级来调节荧光性质的报道，这一结果将为荧光性质的设计开辟新的策略。短句来源合成了具有已知荧光基团、2-氨基苯胺和bpy的缩合结构的7-氨基二吡啶[3,2 -a: 2', 3'-c]吩那嗪（dppz-NH_2），作为一种新的荧光设计概念。结果表明，dppz-NH_2具有较好的荧光特性，表明了该分子设计方法的实用性。Dppz-NH_2与二价阳离子选择性螯合，并伴有荧光反应。此外，Ru-dppz-NH_2配合物是一种高效的光敏单元，易于利用氨基与受体分子结合。证实了dppz-NH_2作为光功能分子的能力。总之，我们开发了一些新的荧光聚吡啶化合物。此外，我们还展示了它们特有的光功能及其作为新型光功能材料的潜力。

Ortho-substitution of the amino amino group was found to produce efficiently fluorescent 2, 2' : 6', 2"-terpyridines (tpy), whose fluorescence were observed around 380 nm. Among them 6-amino tpy showed considerably large fluorescence quantum yield (Φ=0.70). On the other hand, that of 4'-amino tpy was very small (<0.01). We successfully developed the highly fluorescent tpys, and presented that introduction of the amino group (s) at appropriate position (s) is important.4'-phenyltpy (ptp) also exhibited an efficient fluorescence. Substitution at para-position of the phenyl group of ptp showed that amino- and dimethylamino- ptp exhibited a largely red-shifted fluorescence. Solvent dependence of the spectra and MO calculation suggested that introduction of strongly electron donating group elevated the energy level of HOMO-1 over that of HOMO.There have been no reports on tuning the fluorescence property by controlling the energy level of the molecular orbital, and this result would open the way on novel strategy for designing the fluorescence propeties.As a new designing concept of the fluorescent bpy, 7-aminodipyrido [3, 2-a : 2', 3'-c] phenazine (dppz-NH_2), which has condensed structure of the known fluorophore, 2-aminophenazine, and bpy, was synthesized. The result showed an efficient fluorescence of dppz-NH_2 and the usefulness of the new method of the molecular design. Dppz-NH_2 displayed selective chelate formation with divalent cations, and concomitant fluorescence response. Moreover, Ru-dppz-NH_2 complex was found to be an efficient photo-sensitizing unit, and easy to bind with acceptor molecules using the amino group. The ability of dppz-NH_2 as a photo-functional molecule was confirmed.In conclusion, we developed some novel fluorescent polypyridyl compounds. In addition, we showed their characteristic photo-functions and their potentials as novel photo-functional materials.