The development of cost-effective molecular devices that efficiently capture and convert sunlight into other useful forms of energy is a promising approach to meet the world’s increasing energy demands. These devices are designed through a successful combination of materials and molecules that work synergistically to promote light-driven chemical reactions. Light absorption by a surface-bound chromophore triggers a sequence of interfacial electron transfer processes. The efficiencies of the devices are governed by the dynamic balance between the electron transfer reactions that promote energy conversion and undesirable side reactions. Therefore, it is necessary to understand and control these processes to optimize the design of the components of the devices and to achieve higher energy conversion efficiencies. In this context, this review discusses general aspects of interfacial electron transfer reactions in dye-sensitized TiO2 molecular devices for solar energy conversion. A theoretical background on the Marcus-Gerischer theory for interfacial electron transfer and theoretical models for electron transport within TiO2 films are provided. An overview of dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs) is presented, and the electron transfer and transport processes that occur in both classes of devices are emphasized and detailed. Finally, the main spectroscopic, electrochemical and photoelectrochemical experimental techniques that are employed to elucidate the kinetics of the electron transfer reactions discussed in this review are presented.

The photochemistry and photophysics of coordination compounds have been extensively investigated not only because their structure, stability, reactivity dependence on the metal center oxidation state and the coordinated ligand; but also for their electronic transitions in a wide range of visible radiation. The knowledge of light absorption, excited state deactivation, sensitization and quenching processes are crucial to their manipulation aiming the development of systems capable of execute useful functions such as photosensors and/or probes, luminescent devices and molecular systems to convert sunlight into other types of energy. In this review, the progresses and challenges of biomolecules photosensors, organic light emitting diodes and CO2 photoreduction catalysts based on ruthenium(II), rhenium(I) or iridium(III) coordination compounds are discussed based on their photochemical and photophysical processes.

Tris-heteroleptic ruthenium(II) cis-[Ru(Me4-phen)(dcbH2)(NCS)2], where Me4-phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, dcbH2 = 4,4'-dicarboxylic acid 2,2'-bipyridine, was synthesized, purified and characterized. Its characteristics were compared with those determined for cis-[Ru(Me2-phen)(dcbH2)(NCS)2] and cis-[Ru(phen)(dcbH2)(NCS)2] aiming to evaluate the effect of the number of methyl groups on the properties of the compounds. Changes in the Fourier transform infrared (FTIR) and 1H nuclear magnetic resonance (NMR) spectra indicated a modification in the electronic distribution of the complex because of the presence of methyl groups at the 3 and 8 positions of 1,10-phenanthroline. These changes also modified the excited state properties and resulted in a blue shift of the absorption and emission spectra. The complex was incorporated onto TiO2 to prepare dye-sensitized solar cells, achieving up to JSC = 11.9 mA cm–2, VOC = 0.627 V, ff = 0.67 and η = 5.0%.