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Development of Novel Functionalized Organic Fluorescent Materials Having Polypyridyl Structure

具有聚吡啶结构的新型功能化有机荧光材料的研制

基本信息

批准号：
10450339
负责人：
ARAKI Koji
金额：
$ 6.46万
依托单位：
University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

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.

发现氨基的邻位取代可有效地产生荧光2，2'：6'，2”-三联吡啶（tpy），其荧光在380 nm附近观察到。其中6-amino tpy具有较大的荧光量子产率（Φ=0.70）。而4 '-氨基-1，4-二吡啶的相对分子质量则很小（<0.01）。我们成功地开发了高荧光的tpys，并提出了在适当的位置引入氨基的重要性。4 '-苯基tpy（ptp）也表现出有效的荧光。苯基对位取代后，氨基和二甲氨基的ptp荧光强度明显红移。光谱的溶剂依赖性和分子轨道计算表明，强给电子基团的引入使HOMO-1的能级高于HOMO的能级，而通过控制分子轨道能级来调控荧光性质的研究还未见报道，这一结果为荧光性质的设计提供了新的思路。合成了7-氨基二吡啶并[3，2-a：2 '，3'-c]吩嗪（dppz-NH_2），它具有已知荧光团2-氨基吩嗪和联吡啶的缩合结构。结果表明，dppz-NH_2具有良好的荧光性能，说明了分子设计新方法的有效性。Dppz-NH_2显示出与二价阳离子的选择性螯合作用，并伴有荧光响应。此外，Ru-dppz-NH_2配合物是一种有效的光敏化单元，且易于与受体分子结合。dppz-NH_2作为光功能分子的能力得到了证实。总之，我们开发了一些新型的荧光多吡啶化合物。此外，我们还展示了它们特有的光功能和作为新型光功能材料的潜力。