Light-induced Electron Transfer Processes Research Articles

Concerning a hole trap in α-Al2O3:C,Mg

We report the existence of a hole trap in α-Al2O3:C,Mg as determined using thermoluminescence (TL) and optically stimulated luminescence (OSL). The associated experiments are based on the hypotheses that if a TL glow peak is associated with a hole trap in the glow curve of α-Al2O3:C,Mg, that hole trap will not participate in any light-induced electron-transfer process and its removal will not cause the OSL intensity to decrease. To examine the first hypothesis, a TL glow curve was recorded at 1 °C/s to establish the position of glow peaks. There is a high intensity peak at 184 °C (labeled as peak IV) and eight secondary peaks at 48, 80, 108, 228, 288, 320, 386, and 426 °C (peaks I, II, III, and V–IX). The light-induced charge transfer between various electron traps associated with the peaks was studied. This study reveals that all peaks except the one at 228 °C (peak V) participate in the charge-transfer process. A test of the second hypothesis shows that peak V is also not reproduced by illumination (phototransfer), and the depletion of this peak does not influence the charge-transfer process. An additional study on the effect of temperature on the TL and OSL intensity was carried out to further assess the nature of the charge traps associated with the peaks. The depletion of peak V does not affect the OSL intensity. The results from both experiments are clear evidence consistent with the hypothesis that the charge trap associated with peak V is a hole trap.

Cover Feature: Tailoring Quantum Dot Sizes for Optimal Photoinduced Catalytic Activation of Nitrogenase (ChemSusChem 24/2021)

The Cover Feature shows how nanomaterial sizes affect the light-induced electron transfer process with the nitrogenase enzyme. When 2.3 nm CdSe quantum dots are utilized for the photocatalytic hydrogen generation process, an 8-fold increase can be gained as compared with larger-sized quantum dots. Additionally, cysteine-mutated nitrogenase at the electron acceptor side (P-cluster) does not lead to enhanced catalytic performance. More information can be found in the Communication by M. M. Meirovich et al.

Pyrylenes: A New Class of Tunable, Redox-Switchable, Photoexcitable Pyrylium-Carbene Hybrids with Three Stable Redox-States.

A new synthetic and modular access to a large family of redox-switchable molecules based upon the combination of pyrylium salts and carbenes is presented. The redox-properties of this new molecule class correlate very well with the π-accepting properties of the corresponding carbenes. While the pyrylium moiety acts as a chromophore, the carbene moiety can tune the redox-properties and stabilize the corresponding radicals. This leads to the isolation of the first monomeric pyranyl-radical in the solid-state. The three stable oxidation states could be cleanly accessed by chemical oxidation, characterized by NMR, EPR, UV-vis, and X-ray diffraction and supported by (TD)-DFT-calculations. The new hybrid class can be utilized as an electrochemically triggered switch and as a powerful photoexcited reductant. Importantly, the pyrylenes can be used as novel photocatalysts for the reductive activation of aryl halides and sulfonamides by consecutive visible light induced electron transfer processes.

Aerobic Allylation of Alcohols with Non-Activated Alkenes Enabled by Light-Driven Selenium-π-Acid Catalysis

A new organocatalytic protocol for the aerobic dehydrogenative allylation of alcohols using non-activated alkenes as the allylating reagent and ambient air as the terminal oxidant is established. Mechanistically, the procedure relies on the interplay of a diselane and a photo­redox catalyst by means of a light-induced electron transfer process. Under optimized conditions, a broad range of both cyclic and acyclic ethers is accessed with very high functional group tolerance and excellent regioselectivity.

Water Molecules Gating a Photoinduced One-Electron Two-Protons Transfer in a Tyrosine/Histidine (Tyr/His) Model of Photosystem II.

We investigate a biomimetic model of a TyrZ /His190 pair, a hydrogen-bonded phenol/imidazole covalently attached to a porphyrin sensitizer. Laser flash photolysis in the presence of an external electron acceptor reveals the need for water molecules to unlock the light-induced oxidation of the phenol through an intramolecular pathway. Kinetics monitoring encompasses two fast phases with distinct spectral properties. The first phase is related to a one-electron transfer from the phenol to the porphyrin radical cation coupled with a domino two-proton transfer leading to the ejection of a proton from the imidazole-phenol pair. The second phase concerns conveying the released proton to the porphyrin N4 coordinating cavity. Our study provides an unprecedented example of a light-induced electron-transfer process in a TyrZ /His190 model of photosystem II, evidencing the movement of both the phenol and imidazole protons along an isoenergetic pathway.

Inverted-region electron transfer as a mechanism for enhancing photosynthetic solar energy conversion efficiency

In all photosynthetic organisms, light energy is used to drive electrons from a donor chlorophyll species via a series of acceptors across a biological membrane. These light-induced electron-transfer processes display a remarkably high quantum efficiency, indicating a near-complete inhibition of unproductive charge recombination reactions. It has been suggested that unproductive charge recombination could be inhibited if the reaction occurs in the so-called inverted region. However, inverted-region electron transfer has never been demonstrated in any native photosynthetic system. Here we demonstrate that the unproductive charge recombination in native photosystem I photosynthetic reaction centers does occur in the inverted region, at both room and cryogenic temperatures. Computational modeling of light-induced electron-transfer processes in photosystem I demonstrate a marked decrease in photosynthetic quantum efficiency, from 98% to below 72%, if the unproductive charge recombination process does not occur in the inverted region. Inverted-region electron transfer is therefore demonstrated to be an important mechanism contributing to efficient solar energy conversion in photosystem I. Inverted-region electron transfer does not appear to be an important mechanism in other photosystems; it is likely because of the highly reducing nature of photosystem I, and the energetic requirements placed on the pigments to operate in such a regime, that the inverted-region electron transfer mechanism becomes important.

A small electron donor in cobalt complex electrolyte significantly improves efficiency in dye-sensitized solar cells

Photoelectrochemical approach to solar energy conversion demands a kinetic optimization of various light-induced electron transfer processes. Of great importance are the redox mediator systems accomplishing the electron transfer processes at the semiconductor/electrolyte interface, therefore affecting profoundly the performance of various photoelectrochemical cells. Here, we develop a strategy—by addition of a small organic electron donor, tris(4-methoxyphenyl)amine, into state-of-art cobalt tris(bipyridine) redox electrolyte—to significantly improve the efficiency of dye-sensitized solar cells. The developed solar cells exhibit efficiency of 11.7 and 10.5%, at 0.46 and one-sun illumination, respectively, corresponding to a 26% efficiency improvement compared with the standard electrolyte. Preliminary stability tests showed the solar cell retained 90% of its initial efficiency after 250 h continuous one-sun light soaking. Detailed mechanistic studies reveal the crucial role of the electron transfer cascade processes within the new redox system.

Ultrafast Electron Transfer Between Dye and Catalyst on a Mesoporous NiO Surface.

The combination of molecular dyes and catalysts with semiconductors into dye-sensitized solar fuel devices (DSSFDs) requires control of efficient interfacial and surface charge transfer between the components. The present study reports on the light-induced electron transfer processes of p-type NiO films cosensitized with coumarin C343 and a bioinspired proton reduction catalyst, [FeFe](mcbdt)(CO)6 (mcbdt = 3-carboxybenzene-1,2-dithiolate). By transient optical spectroscopy we find that ultrafast interfacial electron transfer (τ ≈ 200 fs) from NiO to the excited C343 ("hole injection") is followed by rapid (t1/2 ≈ 10 ps) and efficient surface electron transfer from C343(-) to the coadsorbed [FeFe](mcbdt)(CO)6. The reduced catalyst has a clear spectroscopic signature that persists for several tens of microseconds, before charge recombination with NiO holes occurs. The demonstration of rapid surface electron transfer from dye to catalyst on NiO, and the relatively long lifetime of the resulting charge separated state, suggests the possibility to use these systems for photocathodes on DSSFDs.

Organized Aggregation Makes Insoluble Perylene Diimide Efficient for the Reduction of Aryl Halides via Consecutive Visible Light-Induced Electron-Transfer Processes.

The consecutive photo-induced electron-transfer (conPET) process found with perylene diimide (PDI) overcomes the limitation of visible-light photocatalysis and sheds light on effective solar energy conversion. By the incorporation of PDI into a metal-organic polymer Zn-PDI, a heterogeneous approach was achieved to tackle the poor solubility and strong tendency to aggregate of PDIs that restricted the exploitation of this outstanding homogeneous process. The interplay between metal-PDI coordination and π···π stacking of the organized PDI arrays in Zn-PDI facilitates the conPET process for the visible light-driven reduction of aryl halides by stabilizing the radical-anion intermediate and catalyst-substrate interacted moiety. These synergistic effects between the PDI arrays and Zn sites further render Zn-PDI photoactivity for fundamental oxidation of benzyl alcohols and amines. The tunable and modular nature of the two-dimensional metal-organic polymers makes the catalyst-embedding strategy promising for the development of ideal photocatalysts toward the better utilization of solar energy.

Reduction of aryl halides by consecutive visible light-induced electron transfer processes

Biological photosynthesis uses the energy of several visible light photons for the challenging oxidation of water, whereas chemical photocatalysis typically involves only single-photon excitation. Perylene bisimide is reduced by visible light photoinduced electron transfer (PET) to its stable and colored radical anion. We report here that subsequent excitation of the radical anion accumulates sufficient energy for the reduction of stable aryl chlorides giving aryl radicals, which were trapped by hydrogen atom donors or used in carbon-carbon bond formation. This consecutive PET (conPET) overcomes the current energetic limitation of visible light photoredox catalysis and allows the photocatalytic conversion of less reactive chemical bonds in organic synthesis.

Photoinduced Electron Transfer Processes of Functionalized Nanocarbons; Fullerenes, Nanotubes and Graphene

To solve the energy demands for a sustainable society, it is crucial to use clean solar energy. Thus, finding methods for efficient light energy conversion is an important scientific goal. For this aim, molecular devices employing composites of nanocarbons such as fullerenes, single wall carbon nanotubes (SWCNTs), and graphene are promising. In this review, we survey light-induced electron-transfer processes of these nanocarbons hybridized with photosensitizers, which have proved to be more favorable than ordinary molecules. Fullerenes connected with suitable electron donors yield characteristic long-lived radical ion pairs, suitable for constructing artificial photosynthetic systems. For SWCNTs, a combination of photosensitizers is also crucial to achieve efficient photo-induced electron transfer processes. Furthermore, in the case of diameter-sorted semi-conductive SWCNTs, each tube can be treated as a “molecule”, thus, allowing molecular orbital calculations to probe the geometry as well as the electronic structures of the photosensitizernanotube hybrids. The two-dimensional graphene has afforded a new reaction field with a wide π-system for the attached molecules. For the confirmation of electron transfer processes, transient absorption methods in the wide wavelength regions have been used effectively. The kinetic data obtained in solution are quite useful to understand the electron transfer mechanisms, which afford useful guiding principles to construct efficient light-energy harvesting devices such as photoelectrochemical and photovoltaic solar cells.

Photoinduced Electron Transfer Facilitates Tautomerization of the Conserved Signaling Glutamine Side Chain in BLUF Protein Light Sensors

The BLUF domain (sensor of blue light using flavin adenine dinucleotide) from a bacterial photoreceptor protein AppA undergoes a cascade of chemical transformations, including hydrogen bond rearrangements around the flavin adenine dinucleotide (FAD) chromophore, in response to light illumination. These transformations are initiated by photoinduced electron and proton transfer from a tyrosine residue to the photoexcited flavin which is assisted by a glutamine residue. According to the recent studies, the proton-coupled electron transfer leads to formation of a radical-pair intermediate Tyr•···FADH• and a tautomeric EE form of glutamine in the ground electronic state. This intermediate is a precursor of the light-induced state of the BLUF photoreceptor implicated in biological signaling. In order to describe evolution of the radical pair, we computed reaction pathways on the ground state potential energy surface employing quantum-chemical calculations in the DFT PBE0/cc-pVDZ approximation for a molecular cluster mimicking the chromophore containing pocket of the AppA BLUF protein. We found a minimum-energy pathway comprised of the following consecutive reaction steps: (1) rotation of the imidic group of the EE glutamine side chain around the Cγ-Cδ bond; (2) flip of the OεH group and formation of the ZE form of the glutamine side chain; and (3) biradical recombination via coupled proton and electron transfer, leading to the ZZ form of the glutamine side chain. The potential-energy barriers for stages 1-3 do not exceed 9 kcal/mol. Energy barrier 3 describing the ZE to ZZ glutamine tautomerization is significantly smaller in the BLUF model than in isolated glutamine, since tautomerization in BLUF is facilitated by electron transfer and radical recombination. Thus, our study shows that tautomerization of the conserved glutamine is coupled to the light-induced electron transfer process in BLUF and, thus, is a viable candidate for the photoactivation mechanism which at present is very much debated.

Gold Nanoparticle-Functionalized Carbon Nanotubes for Light-Induced Electron Transfer Process

The modified electronic properties at the heterojunctions of Au nanoparticle-decorated single-walled carbon nanotubes (SWNTs) have been utilized for photoinduced electron transfer by anchoring a photoactive molecule, namely ruthenium trisbipyridine (Ru(bpy)32+). A unidirectional electron flow was observed from the excited state of Ru(bpy)32+ to carbon nanotubes when the chromophores were linked through Au nanoparticles (SWNT−Au−Ru2+). In contrast, photoinduced electron transfer was not observed from the excited state of Ru(bpy)32+ neither to SWNT nor Au nanoparticles when these components were linked directly. The charge equilibration occurring at the SWNT−Au heterojunctions, due to the differences in electrochemical potentials, result in the formation of a localized depletion layer at the bundled carbon nanotube walls, which may act as acceptor sites of electrons from *Ru(bpy)32+. The charge separation in SWNT−Au−Ru2+ nanohybrids was sustained for several nanoseconds before undergoing recombination, maki...

Visible light induced electron transfer process over nitrogen doped TiO 2 nanocrystals prepared by oxidation of titanium nitride

Nitrogen doped TiO 2 nanocrystals with anatase and rutile mixed phases were prepared by incomplete oxidation of titanium nitride at different temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), core level X-ray photoelectron spectroscopy (CL XPS), valence band X-ray photoelectron spectroscopy (VB XPS), UV–vis diffuse reflectance spectra (UV–vis DRS), and visible light excited photoluminescence (PL). The photocatalytic activity was evaluated for photocatalytic degradation of toluene in gas phase under visible light irradiation. The visible light absorption and photoactivities of these nitrogen doped TiO 2 nanocrystals can be clearly attributed to the change of the additional electronic (N −) states above the valence band of TiO 2 modified by N dopant as revealed by the VB XPS and visible light induced PL. A band gap structure model was established to explain the electron transfer process over nitrogen doped TiO 2 nanocrystals under visible light irradiation, which was consistent with the previous theoretical and experimental results. This model can also be applied to understand visible light induced photocatalysis over other nonmetal doped TiO 2.

Design and Studies on Supramolecular Ferrocene−Porphyrin−Fullerene Constructs for Generating Long-Lived Charge Separated States

Supramolecular ferrocene-porphyrin-fullerene constructs, in which covalently linked ferrocene-porphyrin-crown ether compounds were self-assembled with alkylammonium cation functionalized fullerenes, have been designed to achieve stepwise electron transfer and hole shift to generate long-lived charge separated states. The adopted crown ether-alkylammonium cation binding strategy resulted in stable conjugates as revealed by computational studies performed by the DFT B3LYP/3-21G(*) method in addition to the binding constants obtained from fluorescence quenching studies. The free-energy changes for charge-separation and charge-recombination were varied by the choice of different metal ions in the porphyrin cavity. Free-energy calculations suggested that the light-induced electron-transfer processes from the singlet excited state of porphyrins to be exothermic in all of the investigated supramolecular dyads and triads. Photoinduced charge-separation and charge-recombination processes have been confirmed by the combination of the time-resolved fluorescence and nanosecond transient absorption spectral measurements. In case of the triads, the charge-recombination processes of the radical anion of the fullerene moiety take place in two steps, viz., a direct charge recombination from the porphyrin cation radical and a slower step involving distant charge recombination from the ferrocene cation moiety. The rates of charge recombination for the second route were found to be an order of magnitude slower than the former route, thus fulfilling the condition for charge migration to generate long-lived charge-separated states in supramolecular systems.

Spin Crossover, Liesst, and Niesst-Fascinating Electronic Games in Iron Complexes

Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic structure phenomena depending on the nature of the coordinating ligand sphere. The change of spin state with temperature (thermal spin crossover”) and light-induced electron transfer processes leading to long-lived metastable states are among the most fascinating electronic games encountered in transition metal compounds and are presently under intensive study by chemists and physicists. The first part of this lecture will survey briefly some highlights of previous work and present recent results on thermal spin crossover in iron(II) compounds. The second part of the lecture will focus on selected examples of Light-Induced Excited Spin State Trapping” (LIESST), with special emphasis on the occurrence of bistability and cooperative interactions during LIESST relaxation. The last part of the lecture will be devoted to, Nuclear Decay-Induced Excited Spin State Trapping (NIESST), the unique experiment which allows one to make use of the nuclear disintegration of 57Co → 57Fe as an, internal light source” to generate such photophysical aftereffects as aliovalent charge and anomalous spin states, and to detect and characterize such metastable states simultaneously by time-integral and time-differential Mössbauer emission spectroscopy. Results from lifetime measurements by Mössbauer as well as optical techniques prove that the same relaxation mechanism applies to both phenomena, LIESST and NIESST.

Photophysical and Photochemical Properties of Three-Dimensional Metal-Tris-Oxalate Network Structures

Abstract Chemical variation and combination of metal ions of different valencies in the oxalate backbone as well as in the tris-bpy cation of the three-dimensional network structures of the type [MII 2(ox)3][MII(bpy)3] (bpy = 2,2′-bipyridine, ox = C2O4 2-), [MIMIII(ox)3][MII(bpy)3] and [MIMIII(ox)3][MIII(bpy)3]ClO4 offer unique opportunities for studying a large variety of photophysical processes. Depending upon the relative energies of the excited states of the chromophores, excitation energy transfer either from the tris-bipyridine cation to the oxalate backbone or vice versa is observed, as for instance from [Ru(bpy)3]2+ as photo-sensitiser to [Cr(ox)3]3- as energy acceptor in the combination [NaCr(ox)3][Ru(bpy)3], or from [Cr(ox)3]3- to [Cr(bpy)3]3+ in [NaCr(ox)3][Cr(bpy)3]ClO4. In addition efficient energy migration within the oxalate backbone is observed. Furthermore, depending upon the excited state redox potentials, light-induced electron transfer processes may be envisaged.

Fascinating electronic games in iron complexes

Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic-structure phenomena, depending on the nature of the coordinating ligand sphere. The change of spin state with temperature («thermal spin-crossover»), light-induced electron transfer processes leading to long-lived metastable charge and spin states (e.g., «LIESST» effect), are some of the fascinating electronic games encountered in transition metal compounds, which are presently under extensive study by chemists and physicists. Mossbauer spectroscopy plays a dominant role in the investigation of such phenomena in iron compounds, as will be demonstrated in this paper. This work will focus on selected examples of «thermal spin-crossover» in iron(II) complexes and switching between different spin states by irradiation with light of different wavelength (LIESST effect), demonstrating that Mossbauer spectroscopy besides other physical techniques proves to be a highly elegant tool for following the spin state conversion and the concomitant changes of molecular and crystal structure properties. Finally, Mossbauer emission spectroscopy, both time integral and time differential, has been employed to generate and identify long-lived excited spin states by making use of the nuclear disintegration of 57Co as an intrinsic molecular light source (NIESST=nuclear decay-induced excited-spin-state trapping). Lifetime measurements by optical techniques on LIESST states and by time-differential Mossbauer coincidence spectroscopy on NIESST states prove that the relaxation pathways in the mechanisms for LIESST and NIESST are identical.

High-field/high-frequency EPR/ENDOR — A powerful new tool in photosynthesis research

In photosynthesis research the elucidation of the spatial and electronic structures of the electron donor and acceptor ion radicals is very important for an understanding of the light-induced electron transfer process. Recent 3 mm (W-band, 95 GHz) high-field EPR and ENDOR studies on the primary donor cation radicals P+. (bacteriochlorophyll dimer), the acceptor anion radicals Q+. (quinones), and the charge-separated radical pair (P+.Q−.) in photosynthetic bacteria and biomimetic model systems are presented. From single crystals of, for instance,Rb. sphaeroides R-26 reaction centers both the hyperfine tensors of various protons and theg-tensor of P865 +. have been determined and compared with calculated tensor values based on recent X-ray structure data. The results consistently reveal a breaking of the local C2 symmetry of the electronic structure at the primary donor side of the reaction center. This is of particular interest since it might be relevant for the vectorial electron transfer along the protein complex. Among the quinone radical anions studied are frozen solutions of the electron acceptors of bacterial and plant reaction centers (ubiquinone and plastoquinone, respectively). The increased electron Zeeman interaction in high-field EPR leads to almost completely resolvedg-tensor components even in disordered samples. Theg-tensors and component linewidths are sensitive probes for specific anisotropic interactions with the environment. In the case of the transient correlated coupled radical pair P865 +.-QA −. ofRb. sphaeroides (Fe replaced by Zn) the spin-polarized high-field EPR spectra allow an unambiguous determination of the relative orientation of theg-tensors of the donor and acceptor parts. Thereby high-precision structure information is obtained on the electron transfer pigments after light-induced charge separation.

Light-induced electron transfer in simple and supramolecular Ru-polypyridine complexes

In artificial photosynthesis the chief research goal is to duplicate the function of the photosynthetic unit in nature but not its structural subunits. In this paper, light-induced electron-transfer processes of Ru-polypyridines as energy-storing systems, in the presence of suitable acceptors and catalysts, are described. New highly photostable photosensitizers are presented. A new approach using supramolecular (non-covalently) connected assemblies in addition to covalently linked systems for energy-storing processes is demonstrated. The use of classical and new Ru-complex assemblies in oxygen or hydrogen generation from water is dealt with. The efficiency of the new systems in the reduction of CO2 to methane is presented.