2013 Fiscal Year Annual Research Report
アリールホウ素置換基を有する遷移金属錯体を利用した新規人工光合成系の創製
| Project/Area Number |
13J01659
|
|---|
| Research Institution | Hokkaido University |
|---|
Principal Investigator |
康 媛媛 北海道大学, 大学院総合化学院, 特別研究員(DC1)
|
|---|
| Keywords | photosynthesis system / tricarbonyl rhenium complex / charge transfer unit / CO_2 reduction |
|---|
| Research Abstract |
The developments of an efficient artificial photosynthesis system is one of the most momentous challenges we face today to solve energy security and global warming. Therefore, I aimed at the exploitation of novel photosynthesis systems by using transition metal complexes having arylborane charge transfer units. On the basis of the knowledge hitherto obtained, I designed/synthesized four novel tricarbonyl rhenium(I) complex having a (dimesityl) boryldurylethynyl (DBDE) group at the 4-position of a 1,10-phenanthroline (phen) ligand or a 2,2'-bipyridine (bpy) ligand : fac-[Re(CO)_3(4-DBDE-phen)X] (ReBphenX) and fac-[Re CO)_3(4-DBDE-bpy)X] (ReBbpyX) (X=Br, Cl) and evaluated the spectroscopic, photophysical and especially photoredox properties of the complexes.
All the novel tricarbonyl rhenium(I) complexes having DBDE group showed intense and low-energy absorption, low-energy and long-lived emission compared with the reference complexes without the arylborane unit due to the interactions between MLCT and π(aryl)-p(B) CT.
And then, the photocatalytic CO_2 reduction abilities were studied for all the rhenium(I) complexes. The absorption spectral responses of those rhenium(I) complexes showed that New absorption bands appeared for all the complexes, which may be ascribed to either OER species, dimers, or new products, which will be confirmed after.
The photocatalytic CO_2 reduction by those rhenium(I) complexes were demonstrated and the amounts of CO formed in the photocatalytic reaction were summarized. All the novel rhenium(I) complexes having arylborane charge transfer uni possessed low efficiency for CO_2 photoreduction ability compared with the corresponding complexes without boron unit. This is different with the electrocatalytic ability for CO_2 reduction of them.
|
| Current Status of Research Progress |
Current Status of Research Progress
2: Research has progressed on the whole more than it was originally planned.
Reason
This year I designed and synthesized a series of novel rhenium tricarbonyl and check the photophysical, photochemical and especially photoredox properties of them. However, as I have asked for two months leave due to the birth of my baby. Therefore, from this year, I will start to focus on my research more and continue my experiment.
|
| Strategy for Future Research Activity |
As I have shown before, the photocatalytic efficiency of the novel rhenium(I) tricarbonyl complexes is lower than the corresponding complexes without boron unit, so next at first I plan to synthesize new complexes with more than one arylborane charge transfer units and check the photocatalytic CO_2 ability of them. At last I hope I can find promising candidates for efficient photosensitizers/photocatalysts to give a great impact on the development of artificial photosynthesis systems.
|
Research Products
(2 results)
