A New Class Of Rhenium(I) Diimine Luminophore With Isocyanide Ligands - Molecular Design and Application Studies Towards Solar Energy Conversion
DescriptionThe long-lived phosphorescence and rich excited state properties associated with the metal-to-ligand charge transfer (MLCT) excited state of the rhenium(I) tricarbonyl diimine complexes have been extensively reported. It has been shown that with rational design on the diimine ligand, this class of complexes can be used as a building blocks for many different applications. However, when the diimine ligand is functionalized with a specific functional moiety for the application, tuning of the physical and excited state properties of these complexes is extremely difficult since the carbonyl coligands cannot be derivatized and are inert towards substitution. We have recently shown that by replacing the carbonyl ligands with isoelectronic isocyanide ligands, a new class of luminescent rhenium(I) isocyano diimine complexes can be obtained. By simply varying the electronic and steric features of substituent on the nitrogen atom of the isocyanide ligands, the properties of the corresponding rhenium(I) complexes could be readily modified. In addition, it would also open up the possibility for the extension of the rhenium bipyridine luminophore towards the construction of highly functionalized molecular systems.In this project, new series of rhenium(I) diimine complexes with two, three or four isocyanide ligands in different conformations will be synthesized and characterized. These complexes will be subjected to detailed spectroscopic and electrochemical studies. Moreover, by slight modification of the substituent of the isocyanide ligands, rhenium(I) diimine luminophores with diverse physical and excited state properties could be readily obtained. Through rational design, water-soluble luminophores, photocatalytic and light-harvesting systems will be developed. In summary, the proposed project should contribute to the basic understanding of the photophysics and reactivity of rhenium(I) isocyano diimine complexes. It should also provide insights into the development of photocatalytic system capable of converting solar energy to chemical energy and carrying out useful catalytic reactions.
|Effective start/end date||1/10/10 → 26/01/15|