The Synthesis And Application Of 1,10-phenanthroline Derivatives

1,10-phenanthroline and its derivatives are an important kind of bidentate which contains macrocyclic aromatic conjugation system. Because the nitrogen atoms are located in No. 1 and 10 position which have higher density of electron,so they can integrate with metal ions by stable coordination. These complexes are widely used in metal ion detection, photoelectric materials, sensors, catalysts, medicine and so on. It is very important to design and synthesis phenanthroline derivatives to explore physicial and chemical properties.On the basis of prophase studies in our laboratory,we designed and synthesised 2,9-dialkoxy substituted and 4,7-diaryl substituted 1,10-phenanthroline derivatives. Firstly,Bathophenanthroline(A) was obtained by the reaction of 3-chloro-1-phenyl-1-propanon with 1,2-diaminobenzene under the catalys is of sulfuric acid(the yield was 48.7%). Secondly, quaternization intermidate(B) has been gotten by the reaction of bathophenanthroline and 1,3-dibromopropane with 75.2% yield. Thirdly, lactamine intermidate(C) was formed by the oxidation under the catalys is of potassium ferricyanide with 37.1% yield. Lastly, 2,9-dichloro-4,7-diphenyl-1,10-phenanroline(D) and 2,9-dibromo-4,7-diphenyl-1,10-phenanroline(E) was obtained by chlorination and bromination in the presence of phosphorus pentachloride and phosphorus pentabromide respectively(the yield were 70% and 73.4%).Finally synthesis 2,9-dimethoxy-4,7-diphenyl-1,10- phenanthroline(F), 2,9-diethoxy-4,7-diphenyl-1,10-phenanthroline(G), 2,9-diallyloxy-4,7-di phenyl-1,10-phenanthroline(H), 2,9-diproploxy-4,7-diphenyl-1,10-phena nthroline(I), 2,9-dibutoxy-4,7-diphenyl-1,10-phenanroline(J) by were synthesized by the ether reaction of 2,9-dichloro-4,7-diphenyl-1,10-phenaroline(or2,9-dibromo-4,7-diphenyl-1,10-phenanroline) and sodium methoxide, sodium ethoxide,ect. The yield range from 79.8% to 86.6%.At last, a preliminary study has been conducted on the application of these novel phenanthroline derivatives(, these copper photosensitizers were synthes ized(CuPSD-CuPSJ) by in situ method in water reduction system,using the synthesized 2,9-alkoxy-4,7-diphenyl-1, 10-phenanthroli ne derivatives(D-J) as the N ligands and Xantphos as the P ligands. Their photocatalytic activity of hydrogen generation from water splitting and their photophysical properties were explored and discussed. Compared with CuPSF CuPSH and CuPSI,CuPSJ have lower hydrogen production activity. CuPSG have the highest hydrogen production activity and the turnover number up to 270.