Photocatalytic CO2 Reduction Using Mixed Catalytic Systems Comprising an Iron Cation with Bulky Phenanthroline Ligands.

This study reports on efficient photocatalytic CO2 reduction reactions using mixed catalytic systems of an Fe ion source and various 1,10-phenanthroline derivatives (R1R2p) as ligands in the presence of triethanolamine (TEOA). As the relatively bulky substituents at positions 2 and 9 of R1R2p weakened the ability to coordinate to the Fe ion, the Fe ion formed TEOA complexes. The free R1R2p accepted an electron from the reduced photosensitizer through proton-coupled electron transfer (PCET) using protons of TEOA dissolved in a CH3CN solution in a CO2 atmosphere as the initial step of the catalytic cycle. Although the mixed system of the nonsubstituted 1,10-phenanthroline generates a stable tris(phenanthroline)-Fe(II) complex in solution, this complex could not function as a CO2 reduction catalyst. The mechanism in which R1R2p interacts with the Fe ion after PCET was proposed for this efficient photocatalytic CO2 reduction. The proposed photocatalytic system using the 2,9-di-sec-butyl-phenanthroline ligand could produce CO with high efficiency (quantum yield of 8.2%) combined with a dinuclear Cu(I) complex as a photosensitizer.

Photocatalytic Systems for CO2 Reduction: Metal-Complex Photocatalysts and Their Hybrids with Photofunctional Solid Materials.

ConspectusPhotocatalytic CO2 reduction is a critical objective in the field of artificial photosynthesis because it can potentially make a total solution for global warming and shortage of energy and carbon resources. We have successfully developed various highly efficient, stable, and selective photocatalytic systems for CO2 reduction using transition metal complexes as both photosensitizers and catalysts. The molecular architectures for constructing selective and efficient photocatalytic systems for CO2 reduction are discussed herein. As a typical example, a mixed system of a ring-shaped Re(I) trinuclear complex as a photosensitizer and fac-[Re(bpy)(CO)3{OC2H4N(C2H4OH)2}] as a catalyst selectively photocatalyzed CO2 reduction to CO with the highest quantum yield of 82% and a turnover number (TON) of over 600. Not only rare and noble metals but also earth abundant ones, such as Mn(I), Cu(I), and Fe(II) can be used as central metal cations. In the case using a Cu(I) dinuclear complex as a photosensitizer and fac-Mn(bpy)(CO)3Br as a catalyst, the total formation quantum yield of CO and HCOOH from CO2 was 57% and TONCO+HCOOH exceeded 1300.Efficient supramolecular photocatalysts for CO2 reduction, in which photosensitizer and catalyst units are connected through a bridging ligand, were developed for removing a diffusion control on collisions between a photosensitizer and a catalyst. Supramolecular photocatalysts, in which [Ru(N∧N)3]2+-type photosensitizer and Re(I) or Ru(II) catalyst units are connected to each other with an alkyl chain, efficiently and selectively photocatalyzed CO2 reduction in solutions. Mechanistic studies using time-resolved IR and electrochemical measurements provided molecular architecture for constructing efficient supramolecular photocatalysts. A Ru(II)-Re(I) supramolecular photocatalyst constructed according to this molecular architecture efficiently photocatalyzed CO2 reduction even when it was fixed on solid materials. Harnessing this property of the supramolecular photocatalysts, two types of hybrid photocatalytic systems were developed, namely, photocatalysts with light-harvesting capabilities and photoelectrochemical systems for CO2 reduction.Introduction of light-harvesting capabilities into molecular photocatalytic systems should be important because the intensity of solar light shone on the earth's surface is relatively low. Periodic mesoporous organosilica, in which methyl acridone groups are embedded in the silica framework as light harvesters, was combined with a Ru(II)-Re(I) supramolecular photocatalyst with phosphonic acid anchoring groups. In this hybrid, the photons absorbed by approximately 40 methyl acridone groups were transferred to one Ru(II) photosensitizer unit, and then, the photocatalytic CO2 reduction commenced.To use water as an abundant electron donor, we developed hybrid photocatalytic systems combining metal-complex photocatalysts with semiconductor photocatalysts that display high photooxidation powers, in which two photons are sequentially absorbed by the metal-complex photosensitizer and the semiconductor, resulting in both high oxidation and reduction power. Various types of dye-sensitized molecular photocathodes comprising the p-type semiconductor electrodes and the supramolecular photocatalysts were developed. Full photoelectrochemical cells combining these dye-sensitized molecular photocathodes and n-type semiconductor photoanodes achieved CO2 reduction using only visible light as the energy source and water as the reductant. Drastic improvement of dye-sensitized molecular photocathodes is reported.The results presented in this Account clearly indicate that we can construct very efficient, selective, and durable photocatalytic systems constructed with the metal-complex photosensitizers and catalysts. The supramolecular-photocatalyst architecture in which the photosensitizer and the catalyst are connected to each other is useful especially on the surface of solid owing to rapid electron transfer from the photosensitizer to the catalyst. On basis of these findings, we successfully constructed hybrid systems of the supramolecular photocatalysts with photoactive solid materials. These hybridizations can add new functions to the metal-complex photocatalytic systems, such as water oxidation and light harvesting.

Structural change dynamics of heteroleptic Cu(I) complexes observed by ultrafast emission spectroscopy.

[Cu(I)(dmp)(P)2]+ (dmp = 2,9-dimethyl-1,10-phenanthroline derivatives; P = phosphine ligand) is one of the most promising photosensitizers used in a photo-catalytic system for reducing CO2, for which the quantum yield is as high as 57%. In this work, time-resolved emission spectra of Cu(I) complexes in solutions were investigated using femtosecond fluorescence up-conversion and nanosecond time-resolved emission spectroscopic systems. The temporal profiles of emission intensities less than 10 ps in acetonitrile solution were reproduced using a tri-exponential function with three-time constants of 0.040 ps, 0.78 ps and 8.0 ps. We found that only the second time constant is dependent on the solvent (acetonitrile: 0.78 ps, butyronitrile: 1.4 ps), indicating that the 0.78 ps spectral change is attributed to the structural change of the Cu(I) complex. The oscillator strengths of transition species are derived from the intensities in the time-resolved emission spectra (species-associated spectra). Based on the oscillator strengths, we concluded that the 0.040 ps process is the Sn → S1 internal conversion and the 0.78 ps process is a structural change in the S1 state. The final time constant of 8.0 ps is assigned to the S1 → T1 intersystem crossing because the 3MLCT state (τT1 = 97 ns) is generated after the decay. The DFT calculation showed that the 0.78 ps spectral change (∼600 cm-1 redshift) is attributed to Jahn-Teller distortion around the metal center, and there is a large structural change in the ligand, which results in a large Stokes shift in the Sn state (7.3 × 103 cm-1).

A Molecular Z-Scheme Artificial Photosynthetic System Under the Bias-Free Condition for CO2 Reduction Coupled with Two-electron Water Oxidation: Photocatalytic Production of CO/HCOOH and H2 O2.

Bio-inspired molecular-engineered systems have been extensively investigated for the half-reactions of H2 O oxidation or CO2 reduction with sacrificial electron donors/acceptors. However, there has yet to be reported a device for dye-sensitized molecular photoanodes coupled with molecular photocathodes in an aqueous solution without the use of sacrificial reagents. Herein, we will report the integration of SnIV - or AlIII -tetrapyridylporphyrin (SnTPyP or AlTPyP) decorated tin oxide particles (SnTPyP/SnO2 or AlTPyP/SnO2 ) photoanode with the dye-sensitized molecular photocathode on nickel oxide particles containing [Ru(diimine)3 ]2+ as the light-harvesting unit and [Ru(diimine)(CO)2 Cl2 ] as the catalyst unit covalently connected and fixed within poly-pyrrole layer (RuCAT-RuC2 -PolyPyr-PRu/NiO). The simultaneous irradiation of the two photoelectrodes with visible light resulted in H2 O2 on the anode and CO, HCOOH, and H2 on the cathode with high Faradaic efficiencies in purely aqueous conditions without any applied bias is the first example of artificial photosynthesis with only two-electron redox reactions.

Layered ß-ZrNBr Nitro-Halide as Multifunctional Photocatalyst for Water Splitting and CO2 Reduction.

Developing mixed-anion semiconductors for solar fuel production has inspired extensive interest, but the nitrohalide-based photocatalyst is still in shortage. Here we report a layered nitro-halide ß-ZrNBr with a narrow band gap of ca. 2.3 eV and low defect density to exhibit multifunctionalities for photocatalytic water reduction, water oxidation and CO2 reduction under visible-light irradiation. As confirmed by the results of electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, the formation of anion vacancies in the nitro-halide photocatalyst was inhibited due to its relatively high formation energy. Furthermore, performance of ß-ZrNBr can be effectively promoted by a simple exfoliation into nanosheets to shorten the carrier transfer distance as well as to promote charge separation. Our work extends the territory of functional photocatalysts into the nitro-halide, which opens a new avenue for fabricating efficient artificial photosynthesis.

Utilization of Low-Concentration CO2 with Molecular Catalysts Assisted by CO2-Capturing Ability of Catalysts, Additives, or Reaction Media.

Increasing concentration of atmospheric CO2 is a worldwide concern and continues to trigger various environmental problems. Photo- or electrocatalytic CO2 reduction (CO2-Red) using solar energy, i.e., artificial photosynthesis, is a prospective technique owing to its sustainability and the usefulness of the reaction products. Concentrations of CO2 in exhaust gases from industries are several % to 20%, and that in the atmosphere is about 400 ppm. Although condensation processes of CO2 require high energy consumption and cost, pure CO2 has been used in most of the reported studies for photo- and electrocatalytic CO2-Red because the reaction between CO2 and the catalyst could be one of the rate-limiting steps. To address these issues and provide a repository of potential techniques for other researchers, this perspective summarizes the catalytic systems reported for the reduction of low-concentration CO2, which utilize a combination of catalytic CO2-Red and CO2-capturing reactions (or CO2 adsorption). First, we describe CO2 insertions into M-X bonds of the catalysts, which increase the rate constants and/or equilibrium constants for CO2 binding on the catalysts, and modifications of the second coordination sphere to stabilize the CO2-bound catalysts. Furthermore, we discuss the reaction media used for catalytic CO2-Red that have the unique effect of increasing CO2 concentrations around the catalysts. These reaction media include typical CO2-capturing additives, ionic liquids, and metal-organic frameworks.

Determining Excited-State Structures and Photophysical Properties in Phenylphosphine Rhenium(I) Diimine Biscarbonyl Complexes Using Time-Resolved Infrared and X-ray Absorption Spectroscopies.

We have explored the structural factors on the photophysical properties in two rhenium(I) diimine complexes in acetonitrile solution, cis,trans-[Re(dmb)(CO)2(PPh2Et)2]+ (Et(2,2)) and cis,trans-[Re(dmb)(CO)2(PPh3)2]+ ((3,3)) (dmb = 4,4'-dimethyl-2,2'-bipyridine, Ph = phenyl, Et = ethyl) using the combination method of time-resolved infrared spectroscopy, time-resolved extended X-ray absorption fine structure, and quantum chemical calculations. The difference between these complexes is the number of phenyl groups in the phosphine ligand, and this only indirectly affects the central Re(I). Despite this minor difference, the complexes exhibit large differences in emission wavelength and excited-state lifetime. Upon photoexcitation, the bond length of Re-P and angle of P-Re-P are significantly changed in both complexes, while the phenyl groups are largely rotated by ∼20° only in (3,3). In contrast, there is little change in charge distribution on the phenyl groups when Re to dmb charge transfer occurs upon photoexcitation. We concluded that the instability from steric effects of phenyl groups and diimine leads to a smaller Stokes shift of the lowest excited triplet state (T1) in (3,3). The large structural change between the ground and excited states causes the longer lifetime of T1 in (3,3).

Photocatalysis of a Dinuclear Ru(II)-Re(I) Complex for CO2 Reduction on a Solid Surface.

The development of CO2-reduction photocatalysts is one of the main targets in the field of artificial photosynthesis. Recently, numerous hybrid systems in which supramolecular photocatalysts comprised of a photosensitizer and catalytic-metal-complex units are immobilized on inorganic solid materials, such as semiconductors or mesoporous organosilica, have been reported as CO2-reduction photocatalysts for various functions, including water oxidation and light harvesting. In the present study, we investigated the photocatalytic properties of supramolecular photocatalysts comprised of a Ru(II)-complex photosensitizer and a Re(I)-complex catalyst fixed on the surface of insulating Al2O3 particles: the distance among the supramolecular photocatalyst molecules should be fixed. Visible-light irradiation of the photocatalyst in the presence of an electron donor under a CO2 atmosphere produced CO selectively. Although CO formation was also observed for a 1:1 mixture of mononuclear Ru(II) and Re(I) complexes attached to an Al2O3 surface, the photocatalytic activity was much lower. The activity of the Al2O3-supported photocatalyst was strongly dependent on the adsorption density of the supramolecular moiety, where the initial rate of photocatalytic CO formation was faster at lower density and higher photocatalyst durability was achieved at higher density. One of the main reasons for the former phenomenon is the decreased quenching fraction of the excited state of the photosensitizer unit by the reductant dissolved in the solution phase in the case of higher density. This is due to the self-quenching of the excited photosensitizer unit and steric hindrance between the condensed supramolecular photocatalyst molecules attached to the surface. The higher durability of the more condensed system is caused by intermolecular electron transfer between reduced supramolecular photocatalyst molecules, which accelerates the formation of CO in the photocatalytic CO2 reduction. Coadsorption of a Ru(II) mononuclear complex as a redox photosensitizer could drastically reinforce the photocatalysis of the supramolecular photocatalyst on the surface of the Al2O3 particles: more than 10 times higher turnover number and about 3.4 times higher turnover frequency of CO formation. These investigations provide new architectures for the construction of efficient and durable hybrid photocatalytic systems for CO2 reduction, which are composed of metal-complex photocatalysts and solid materials.

Efficient Visible-Light-Driven CO2 Reduction by a Cobalt Molecular Catalyst Covalently Linked to Mesoporous Carbon Nitride.

Achieving visible-light-driven carbon dioxide reduction with high selectivity control and durability while using only earth abundant elements requires new strategies. Hybrid catalytic material was prepared upon covalent grafting a Co-quaterpyridine molecular complex to semiconductive mesoporous graphitic carbon nitride (mpg-C3N4) through an amide linkage. The molecular material was characterized by various spectroscopic techniques, including XPS, IR, and impedance spectroscopy. It proved to be a selective catalyst for CO production in acetonitrile using a solar simulator with a high 98% selectivity, while being remarkably robust since no degradation was observed after 4 days of irradiation (ca. 500 catalytic cycles). This unique combination of a selective molecular catalyst with a simple and robust semiconductive material opens new pathways for CO2 catalytic light-driven reduction.

An Artificial Z-Scheme Constructed from Dye-Sensitized Metal Oxide Nanosheets for Visible Light-Driven Overall Water Splitting.

Sensitization of a wide-gap oxide semiconductor with a visible-light-absorbing dye has been studied for decades as a means of producing H2 from water. However, efficient overall water splitting using a dye-sensitized oxide photocatalyst has remained an unmet challenge. Here we demonstrate visible-light-driven overall water splitting into H2 and O2 using HCa2Nb3O10 nanosheets sensitized by a Ru(II) tris-diimine type photosensitizer, in combination with a WO3-based water oxidation photocatalyst and a triiodide/iodide redox couple. With the use of Pt-intercalated HCa2Nb3O10 nanosheets further modified with amorphous Al2O3 clusters as the H2 evolution component, the dye-based turnover number and frequency for H2 evolution reached 4580 and 1960 h-1, respectively. The apparent quantum yield for overall water splitting using 420 nm light was 2.4%, by far the highest among dye-sensitized overall water splitting systems reported to date. The present work clearly shows that a carefully designed dye/oxide hybrid has great potential for photocatalytic H2 production, and represents a significant leap forward in the development of solar-driven water splitting systems.

Factors determining formation efficiencies of one-electron-reduced species of redox photosensitizers.

Improvement in the photochemical formation efficiency of one-electron-reduced species (OERS) of a photoredox photosensitizer (a redox catalyst) is directly linked to the improvement in efficiencies of the various photocatalytic reactions themselves. We investigated the primary processes of a photochemical reduction of two series [Ru(diimine)3]2+ and [Os(diimine)3]2+ as frequently used redox photosensitizers (PS2+), by 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as a typical reductant in detail using steady-irradiation and time-resolved spectroscopies. The rate constants of all elementary processes of the photochemical reduction of PS2+ by BIH to give the free PS•+ were obtained or estimated. The most important process for determining the formation efficiency of the free PS•+ was the escape yield from the solvated ion pair [PS•+-BIH•+], which was strongly dependent on both the central metal ion and the ligands. In cases with the same central metal ion, the system with larger -ΔGbet, which is the free energy change in the back-electron transfer from the OERS of PS•+ to BIH•+, tended to lower the escape yield of the free OERS of PS2+. On the other hand, different central metal ions drastically affected the escape yield even in cases with similar -ΔGbet; the escape yield in the case of RuH2+ (-ΔGbet = 1.68 eV) was 5-11 times higher compared to those of OsH2+ (-ΔGbet = 1.60 eV) and OsMe2+ (-ΔGbet = 1.71 eV). The back-electron transfer process from the free PS•+ to the free BIH•+ could not compete against the further reaction of the free BIH•+, which is the deprotonation process giving BI•, in DMA for all examples. The produced BI• gave one electron to PS2+ in the ground state to give another PS•+, quantitatively. Based on these findings and investigations, it is clarified that the photochemical formation efficiency of the free PS•+ should be affected not only by -ΔGbet but also by the heavy-atom effect of the central metal ion, and/or the oxidation power of the excited PS2+, which should determine the distance between the excited PS and BIH at the moment of the electron transfer.

Earth-Abundant Molecular Z-Scheme Photoelectrochemical Cell for Overall Water-Splitting.

A push-pull organic dye and a cobaloxime catalyst were successfully cografted on NiO and CuGaO2 to form efficient molecular photocathodes for H2 production with >80% Faradaic efficiency. CuGaO2 is emerging as a more effective p-type semiconductor in photoelectrochemical cells and yields a photocathode with 4-fold higher photocurrent densities and 400 mV more positive onset photocurrent potential compared to the one based on NiO. Such an optimized CuGaO2 photocathode was combined with a TaON|CoO x photoanode in a photoelectrochemical cell. Operated in this Z-scheme configuration, the two photoelectrodes produced H2 and O2 from water with 87% and 88% Faradaic efficiency, respectively, at pH 7 under visible light and in the absence of an applied bias, equating to a solar to hydrogen conversion efficiency of 5.4 × 10-3%. This is, to the best of our knowledge, the highest efficiency reported so far for a molecular-based noble metal-free water splitting Z-scheme.

Synthesis of an Emissive Spectacle-Shaped Hexanuclear Rhenium(I) Complex.

Ring-shaped multinuclear Re(I) complexes (Re(I) rings) have the potential to function as useful units in multifarious photofunctional compounds because of their flexibility in molecular design and various photofunctions. The first synthetic example of the coupling reaction using a Re(I) ring as a building block to synthesize a novel spectacle-shaped hexanuclear complex is reported herein. This complex shows an efficient intramolecular energy transfer to accumulate the excitation energy into the central Re(I) units, and has suitable photophysical properties as a photosensitizer.

Kinetics and Mechanism of Intramolecular Electron Transfer in Ru(II)-Re(I) Supramolecular CO2-Reduction Photocatalysts: Effects of Bridging Ligands.

The supramolecular photocatalysts in which a Ru(II) complex as a molecular redox photosensitizer unit and a Re(I) complex as a molecular catalyst unit are connected with a various alkyl or ether chain have attracted attention because they can efficiently photocatalyze CO2 reduction with high durability and high selectivity of CO formation, especially on various solid materials such as semiconductor electrodes and mesoporous organosilica. The intramolecular electron transfer from the one-electron reduced photosensitizer unit to the catalyst unit, which follows excitation of the photosensitizer unit and subsequent reductive quenching of the excited photosensitizer unit by a reductant, is one of the most important processes in the photocatalytic reduction of CO2. We succeeded in determining the rate constants of this intramolecular electron transfer process by using subnanosecond time-resolved IR spectroscopy. The logarithm of rate constants shows a linear relationship with the lengths of the bridging chain in the supramolecular photocatalysts with one bridging alkyl or ether chain. In conformity with the exponential decay of the wave function and the coupling element in the long-distance electron transfer, the apparent decay coefficient factor (ß) in the supramolecular photocatalysts with one bridging chain was determined to be 0.74 Å-1. In the supramolecular photocatalyst with two ethylene chains connecting between the photosensitizer and catalyst units, on the other hand, the intramolecular electron transfer rate is much faster than that with only one ethylene chain. These results strongly indicate that the intramolecular electron transfer from the one-electron reduced species of the Ru photosensitizer unit to the Re catalyst unit proceeds by the through-bond mechanism.

A Carbon Nitride/Fe Quaterpyridine Catalytic System for Photostimulated CO2-to-CO Conversion with Visible Light.

Efficient and selective photostimulated CO2-to-CO reduction by a photocatalytic system consisting of an iron-complex catalyst and a mesoporous graphitic carbon nitride (mpg-C3N4) redox photosensitizer is reported for the first time. Irradiation in the visible region (λ ≥ 400 nm) of an CH3CN/triethanolamine (4:1, v/v) solution containing [Fe(qpy)(H2O)2]2+ (qpy = 2,2':6',2'':6'',2''-quaterpyridine) and mpg-C3N4 resulted in CO evolution with 97% selectivity, a turnover number of 155, and an apparent quantum yield of ca. 4.2%. This hybrid catalytic system, comprising only earth abundant elements, opens new perspectives for solar fuels production using CO2 as a renewable feedstock.

Highly Efficient and Robust Photocatalytic Systems for CO2 Reduction Consisting of a Cu(I) Photosensitizer and Mn(I) Catalysts.

The development of highly efficient, selective, and durable photocatalytic CO2 reduction systems that only use earth-abundant elements is key for both solving global warming and tackling the shortage of energy and carbon resources. Here, we successfully developed CO2 reduction photocatalysts using [Cu2(P2bph)2]2+ (CuPS) (P2bph = 4,7-diphenyl-2,9-di(diphenylphosphinotetramethylene)-1,10-phenanthroline) as a redox photosensitizer and fac-Mn(X2bpy)(CO)3Br (Mn(4X)) (X2bpy = 4,4'-X2-2,2'-bipyridine (X = -H and -OMe) or Mn(6mes) (6mes = 6,6'-(mesityl)2-2,2'-bipyridne)) as the catalyst. The most efficient photocatalysis was achieved by Mn(4OMe): The total quantum yield of CO2 reduction products was 57%, the turnover number based on the Mn catalyst was over 1300, and the selectivity of CO2 reduction was 95%. Electronic and steric effects of the substituents (X) in the Mn complexes largely affected both the photocatalytic efficiency and the product selectivity. For example, the highest selectivity of CO formation was achieved by using Mn(6mes) (selectivity SCO = 96.6%), whereas the photocatalytic system using Mn(4H) yielded HCOOH as the main product ( SHCOOH = 74.6%) with CO and H2 as minor products ( SCO = 23.7%, SH2 = 1.7%). In these photocatalytic reactions, CuPS played its role as an efficient and very durable redox photosensitizer, while remaining stable in the reaction solution even after a turnover number of 200 had been reached (the catalyst used had a turnover number of over 1000).

A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction.

Mixed anion compounds such as oxynitrides and oxychalcogenides are recognized as potential candidates of visible-light-driven photocatalysts since, as compared with oxygen 2p orbitals, p orbitals of less electronegative anion (e.g., N3-, S2-) can form a valence band that has more negative potential. In this regard, oxyfluorides appear unsuitable because of the higher electronegativity of fluorine. Here we show an exceptional case, an anion-ordered pyrochlore oxyfluoride Pb2Ti2O5.4F1.2 that has a small band gap (ca. 2.4 eV). With suitable modification of Pb2Ti2O5.4F1.2 by promoters such as platinum nanoparticles and a binuclear ruthenium(II) complex, Pb2Ti2O5.4F1.2 worked as a stable photocatalyst for visible-light-driven H2 evolution and CO2 reduction. Density functional theory calculations have revealed that the unprecedented visible-light-response of Pb2Ti2O5.4F1.2 arises from strong interaction between Pb-6s and O-2p orbitals, which is enabled by a short Pb-O bond in the pyrochlore lattice due to the fluorine substitution.

Modulation of the Photophysical, Photochemical, and Electrochemical Properties of Re(I) Diimine Complexes by Interligand Interactions.

The photophysical and photochemical properties of transition metal complexes have attracted considerable attention because of their recent applications as photocatalysts in artificial photosynthesis and organic synthesis, as light emitters in electroluminescent (EL) devices, and as dyes in solar cells. The general control methods cannot be always used to obtain transition metal complexes with photochemical properties that are suitable for the above-mentioned applications. In the fields of solar energy conversion, strong metal-to-ligand charge-transfer (MLCT) absorption of redox photosensitizers and/or photocatalysts in the visible region with long wavelength is essential. However, the usual methods, i.e., introduction of electron-withdrawing groups into the electron-accepting ligand and/or weak-field ligands into the central metal, have several drawbacks, including shorter excited-state lifetime, lower emission efficiency, and lower oxidation and reduction power. Herein we describe a new method to control the photophysical, photochemical, and electrochemical properties of Re(I) diimine carbonyl complexes that have been widely used in various fields such as photocatalysts for CO2 reduction and emitters in EL devices and sensors. This method involves the introduction of interligand interactions (π-π and CH-π interactions) into the Re(I) complexes; the aromatic diimine ligand coordinating to the Re center approaches the aryl groups on the phosphine ligand or ligands at the cis position, which "compulsorily" induces a weak interaction between these aromatic groups. As a result of this interligand interaction, the Re complexes with the aromatic diimine ligand and the arylphosphine ligand(s) exhibit red-shifted 1MLCT absorption but afford blue-shifted emission from the triplet metal-to-ligand charge-transfer (3MLCT) excited state. This increases the oxidation power and lifetime of the 3MLCT excited state. These unique property changes are favorable, particularly for redox photosensitizers. The interligand interaction is strongly expressed by the ring-shaped multinuclear Re(I) complexes (Re-rings). In the case of Re-rings with high steric hindrance due to a small inner cavity, the lifetime of the 3MLCT excited state is up to 8 µs and the emission quantum yield is up to 70%. These properties cannot be obtained by the corresponding mononuclear Re(I) complexes, which generally exhibit shorter lifetimes (<1 µs) and lower emission quantum yields (<10%). Some of the Re-rings could be successfully applied as efficient photosensitizers in photocatalytic systems for CO2 reduction; the highest quantum yields for CO2 reduction were achieved by using photocatalytic systems composed of Re-rings as the photosensitizers and Re(I) (82%), Ru(II) (58%), and Mn(I) (48%) complexes as catalysts. This interligand interaction potentially provides unique and useful methods for controlling the photophysical, photochemical, and electrochemical functions of various metal complexes, paving the way to create new functions for metal complexes.

Synthesis of Re(I) Rings Comprising Different Re(I) Units and Their Light-Harvesting Abilities.

Trimethylamine N-oxide (Me3NO) could selectively remove only one CO ligand from fac-[Re(N^N)(CO)3(PR2R')]+ (N^N = diimine ligand), whereby only the CO ligand in the trans position to the phosphorus ligand was selectively removed to give cis,trans-[ReI(N^N)(CO)2(PR2R')(L)] n+ in good yields. This decarbonylation reaction using Me3NO was found to be especially useful for synthesizing biscarbonyl Re(I) complexes with electron-withdrawing groups in the diimine ligand, which could not be synthesized or were obtained only in low yields by the photochemical method. Me3NO also selectively removed the carbonyl ligands in the trans position to the phosphorus ligands from the edge Re(I) complex units, which have the fac-[Re(N^N)(CO)3(PR2R')]+ structure, in linear-shaped Re(I) multinuclear complexes. This reaction was successfully applied to synthesize a novel precursor with ring-shaped multinuclear Re complexes (Re-rings) comprising different kinds of Re(I) units. The newly synthesized Re-rings, which consist of one Re unit with a 4,4'-bis(trifluoromethyl)-2,2'-bipyridine (CF3bpy) ligand and one or two Re unit(s) with a 2,2'-bipyridine (bpy) ligand, showed almost quantitative excitation-energy harvesting ability from the Re unit(s) with bpy to that with CF3bpy.