LOW POWER UPCONVERSION FOR SOLAR FUELS PHOTOCHEMISTRY

Castellano, Felix N.¹ 

[1]Bowling Green State University

关键词: Photochemistry;    Upconversion;    Solar Fuels;    Time-resolved Spectroscopy;    Energy Transfer;   

DOI  :  10.2172/1089302
RP-ID  :  DOE/SC0008614-1
PID  :  OSTI ID: 1089302
Others  :  Other: DE-FG02-12ER16348

学科分类：再生能源与代替技术

美国|英语

来源: SciTech Connect

【 摘 要 】

Earth abundant copper(I) diimine complexes represent a renewable and economically feasible alternative to commonly used heavy metal containing chromophores. In the metal-to-ligand charge transfer (MLCT) excited state, copper(I) diimine complexes typically undergo a significant structural rearrangement, leading to molecules with large Stokes shifts and very short excited state lifetimes, thereby limiting their usefulness as sensitizers in bimolecular electron and triplet energy transfer reactions. Strategically placed bulky substituents on the coordinating phenanthroline ligands have proven useful in restricting the transiently produced excited state Jahn-Teller distortion, leading to longer-lived excited states. By combining bulky sec-butyl groups in the 2- and 9- positions with methyl groups in the 3-,4-, 7-, and 8- positions, a remarkably long-lived (2.8 ??s in DCM) copper(I) bis-phenanthroline complex, [Cu(dsbtmp)2]+, has been synthesized and characterized. Unlike other copper(I) diimine complexes, [Cu(dsbtmp)2]+ also retains a ??s lifetime in coordinating solvents such as acetonitrile and water as a result of the cooperative sterics inherent in the molecular design. Preliminary results on the use of this complex in hydrogen-forming homogeneous photocatalysis is presented. Photon upconversion based on sensitized triplet-triplet annihilation (TTA) represents a photochemical means to generate high-energy photons (or high-energy chemical products) from low-energy excitation, having potential applications in solar energy conversion and solar fuels producing devices. For the first time, synthetically facile and earth abundant Cu(I) MLCT sensitizers have been successfully incorporated into two distinct photochemical upconversion schemes, affording both red-to-green and orange-to-blue wavelength conversions. Preliminary results on aqueous-based photochemical upconversion as well as intramolecular Sn(IV) porphyrins containing axially coordinated aromatic hydrocarbon chromophores poised for upconversion photochemistry are also presented.