Abstract
This review summarizes investigations carried out at the Laboratory of Photochemistry and Energy Conversion (LFCE) in the University of Sao Paulo dealing with design and characterization of ruthenium(II), rhenium(I) and iridium(III) polypyridine complexes with desired photochemical and photophysical properties in light of the development of optoelectronics and photoinduced energy conversion systems. First, the breakthroughs on molecular engineering of emissive ReI, RuII and IrIII complexes for the development of highly efficient light-emitting devices, such as organic light-emitting diodes (OLEDs) and light-emitting electrochemical cells (LECs), are presented. Then, the photochemical and photophysical properties of fac-[Re(CO)3(NN)(trans-L)]+ complexes (NN = bidentate polypyridyl ligands and trans-L = stilbene-like ligand), which find use in molecular machines and photosensors, are discussed. Finally, dye-sensitized energy conversion devices based on RuII complexes and natural dyes, such as dye-sensitized solar cells (DSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs), are reviewed, highlighting some strategies for photoanode engineering aiming at improved device efficiencies.
Highlights
In sub-section 2.2 are effective in sensitizing the trans⇌cis photoisomerization of stilbene-like molecules, Figure 12.6,79,117‐142 This photochemical reaction is appealing for allowing molecular geometry control by means of light absorption,[5,143] which can be conveniently exploited in molecular machines, gears and motors with yes-no or on-off logical responses for applications in sensors and biological systems, such as deoxyribonucleic acid (DNA) transcription[144] and regulation of cations in membranes.[145,146,147]
From other photovoltaic technologies, dye-sensitized solar cells (DSCs) are photoelectrochemical cells in which light-to-electricity conversion occurs via dyes chemically adsorbed on the electrode surface and the separation of charge carriers is kinetically controlled by the chemical reaction involved.[162,163]
DSCs sensitized by mulberry exhibited constant photoelectrochemical parameters after 14 weeks of continuous evaluation, remaining stable even after 36 weeks with a fairly good efficiency when sealed under proper condition.[198]
Summary
A supramolecular approach gives rise to the design of organized systems and can be conveniently exploited through metal complexes for the control of photoproperties and development of molecular devices through structurally organized and functionally integrated chemical systems.[1,2,3,4,5] One of the strategies is the use of coordination compounds with proper ligands to pursue a high chemical stability and intense absorption in the visible[6,7] with suitable redox properties for energy and/or electron transfer processes.[8,9,10,11,12]. We show that these compounds are strategical for the development of such supramolecular devices as they can exhibit a high chemical stability and intense absorption in the visible due to metal-to-ligand charge transfer (1MLCT) transitions,[6,7] with suitable redox properties for energy and/or electron transfer processes.[8,9,10,11,12] Some of these complexes exhibit intense luminescence at room temperature, usually ascribed to a phosphorescence from the 3MLCT counterpart arisen from a high spin-orbit coupling (SOC).[29,30,31]
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