Supramolecular multi-electron redox photosensitisers comprising a ring-shaped Re(i) tetranuclear complex and a polyoxometalate.

Redox photosensitisers (PSs) play essential roles in various photocatalytic reactions. Herein, we synthesised new redox PSs of 1 : 1 supramolecules that comprise a ring-shaped Re(i) tetranuclear complex with 4+ charges and a Keggin-type heteropolyoxometalate with 4- charges. These PSs photochemically accumulate multi-electrons in one molecule (three or four electrons) in the presence of an electron donor and can supply electrons with different reduction potentials. PSs were successfully applied in the photocatalytic reduction of CO2 using catalysts (Ru(ii) and Re(i) complexes) and triethanolamine as a reductant. In photocatalytic reactions, these supramolecular PSs supply a different number of electrons to the catalyst depending on the redox potential of the intermediate, which is made from the one-electron-reduced species of the catalyst and CO2. Based on these data, information on the reduction potentials of the intermediates was obtained.

Ion-pairing π-electronic systems: ordered arrangement and noncovalent interactions of negatively charged porphyrins.

In this study, charged π-electronic species are observed to develop stacking structures based on electrostatic and dispersion forces. i π- i π Interaction, defined herein, functions for the stacking structures consisting of charged π-electronic species and is in contrast to conventional π-π interaction, which mainly exhibits dispersion force, for electronically neutral π-electronic species. Establishing the concept of i π- i π interaction requires the evaluation of interionic interactions for π-electronic ion pairs. Free base (metal-free) and diamagnetic metal complexes of 5-hydroxy-10,15,20-tris(pentafluorophenyl)porphyrin were synthesized, producing π-electronic anions upon the deprotonation of the hydroxy unit. Coexisting cations in the ion pairs with porphyrin anions were introduced as the counter species of the hydroxy anion as a base for commercially available cations and as ion-exchanged species, via Na+ in the intermediate ion pairs, for synthesized π-electronic cations. Solid-state ion-pairing assemblies were constructed for the porphyrin anions in combination with aliphatic tetrabutylammonium (TBA+) and π-electronic 4,8,12-tripropyl-4,8,12-triazatriangulenium (TATA+) cations. The ordered arrangements of charged species, with the contributions of the charge-by-charge and charge-segregated modes, were observed according to the constituent charged building units. The energy decomposition analysis (EDA) of single-crystal packing structures revealed that electrostatic and dispersion forces are important factors in stabilizing the stacking of π-electronic ions. Furthermore, crystal-state absorption spectra of the ion pairs were correlated with the assembling modes. Transient absorption spectroscopy of the single crystals revealed the occurrence of photoinduced electron transfer from the π-electronic anion in the charge-segregated mode.

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).

NH Tautomerism of N-Confused Porphyrin: Solvent/Substituent Effects and Isomerization Mechanism.

The effects of substituents and solvents on the NH tautomerism of N-confused porphyrin (2) were investigated. The structures, electronic states, and aromaticity of NH tautomers (2-2H and 2-3H) were studied by absorption and nuclear magnetic resonance (1H, 13C, and 15N) spectroscopies, single-crystal X-ray diffraction analysis, and theoretical calculations. The relative stability of the tautomers is highly affected by solvents, with the 3H-type tautomer being more stable in nonpolar solvents, while the 2H-type tautomer being highly stabilized in polar solvents with high donor numbers such as N,N-dimethylformamide (DMF), pyridine, and acetone. Electron-withdrawing groups on the meso-aryl substituents as well as the methyl group at the ortho position also stabilize the 2H-type tautomer. Kinetically, the tautomerism rate is significantly influenced by solvent and concentration, and a particularly large activation entropy (ΔS⧧) is obtained in pyridine. The first-order deuterium isotope effect on the reaction rates of NH tautomerism (kH/kD) is determined to be 2.4 at 298 K. On the basis of kinetic data, the mechanism of isomerization is identified as an intramolecular process, including the rotation of the confused pyrrole in pyridine/chloroform and DMF/chloroform mixed solvent systems, and as a pyridine-mediated process in pyridine alone.

Realization of red shift of absorption spectra using optical near-field effect.

In many applications such as CO2 reduction and water splitting, high-energy photons in the ultraviolet region are required to complete the chemical reactions. However, to realize sustainable development, the photon energies utilized must be lower than the absorption edge of the materials including the metal complex for CO2 reduction, the electrodes for water splitting, because of the huge amount of lower energy than the visible region received from the sun. In the previous works, we had demonstrated that optical near-fields (ONFs) could realize chemical reactions, by utilizing photon energies much lower than the absorption edge because of the spatial non-uniformity of the electric field. In this paper, we demonstrate that an ONF can realize the red shift of the absorption spectra of the metal-complex material for photocatalytic reduction. By attaching the metal complex to ZnO nano-crystalline aggregates with nano-scale protrusions, the absorption spectra by using diffuse reflection of the metal complex can be shifted to a longer wavelength by 10.6 nm. The results of computational studies based on a first-principles computational program including the ONF effect provide proof of the increase in the absorption of the metal complex at lower photon energies. Since the near-field assisted field increase improves the carrier excitation in the metal-complex materials, this effect may be universal and it could applicable to CO2 reduction using the other metal-complex materials, as well as to the other photo excitation process including water splitting.

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.

Photocatalytic Reduction of Low Concentration of CO2.

A novel molecular photocatalytic system with not only high reduction ability of CO2 but also high capture ability of CO2 has been developed using a Ru(II)-Re(I) dinuclear complex as a photocatalyst. By using this photocatalytic system, CO2 of 10% concentration could be selectively converted to CO with almost same photocatalysis to that under a pure CO2 atmosphere (TONCO > 1000, ΦCO > 0.4). Even 0.5% concentration of CO2 was reduced with 60% initial efficiency of CO formation by using the same system compared to that using pure CO2 (TONCO > 200). The Re(I) catalyst unit in the photocatalyst can efficiently capture CO2, which proceeds CO2 insertion to the Re-O bond, and then reduce the captured CO2 by using an electron supplied from the photochemically reduced Ru photosensitizer unit.

Doubly N-Methylated Porphyrinoids.

Chirality-induced aromatic π-electronic macrocycles, porphyrin and corroles, were synthesized through doubly inner N-methylation through multistep and one-pot reactions, respectively. The exact structures of doubly N-methylated porphyrin and corroles were revealed by single-crystal synchrotron X-ray analysis, exhibiting two N-methyl groups located on neighboring pyrrole rings in up/down conformations. These doubly inner N-substitutions of the π-electronic macrocycles induced distorted geometries, resulting in chiroptical properties after optical resolutions.

High catalytic abilities of binuclear rhenium(i) complexes in the photochemical reduction of CO2 with a ruthenium(ii) photosensitiser.

Photocatalytic systems for CO2 reduction using a Ru(ii) tris-diimine complex (Ru) as a photosensitiser and dinuclear Re(i) diimine tricarbonyl complexes (Re(n)Re), in which diimine ligands are connected by alkyl chains of various lengths (-CnH2n-: n = 2, 3, 4, 6, 14), as catalysts were investigated. The photocatalytic systems using Re(n)Re exhibited improved durability compared with that using the corresponding mononuclear Re(i) complex (Re); moreover, among the Re(n)Re, shorter alkyl chains in the bridging ligands induced greater durability. We found that the durability of the photocatalytic system depended on the decomposition speed of Ru, which could be suppressed using Re(n)Re with shorter alkyl chains.

Synthesis of novel photofunctional multinuclear complexes using a coupling reaction.

Various photofunctional metal complexes with functional groups, i.e. bromo and vinyl groups, were integrated into hetero-multinuclear complexes using the Mizoroki-Heck reaction. The obtained trinuclear complexes absorb a wide range of visible light and have a long excited state lifetime and the photocatalytic ability to obtain CO2 reduction.

Photocatalytic CO2 reduction to formic acid using a Ru(II)-Re(I) supramolecular complex in an aqueous solution.

In an aqueous solution, photophysical, photochemical, and photocatalytic abilities of a Ru(II)-Re(I) binuclear complex (RuReCl), of which Ru(II) photosensitizer and Re(I) catalyst units were connected with a bridging ligand, have been investigated in details. RuReCl could photocatalyze CO2 reduction using ascorbate as an electron donor, even in an aqueous solution. The main product of the photocatalytic reaction was formic acid in the aqueous solution; this is very different in product distribution from that in a dimethylformamide (DMF) and triethanolamine (TEOA) mixed solution in which the main product was CO. A (13)CO2 labeling experiment clearly showed that formic acid was produced from CO2. The turnover number and selectivity of the formic acid production were 25 and 83%, respectively. The quantum yield of the formic acid formation was 0.2%, which was much lower, compared to that in the DMF-TEOA mixed solution. Detail studies of the photochemical electron-transfer process showed back-electron transfer from the one-electron-reduced species (OERS) of the photosensitizer unit to an oxidized ascorbate efficiently proceeded, and this should be one of the main reasons why the photocatalytic efficiency was lower in the aqueous solution. In the aqueous solution, ligand substitution of the Ru(II) photosensitizer unit proceeded during the photocatalytic reaction, which was a main deactivation process of the photocatalytic reaction. The product of the ligand substitution was a Ru(II) bisdiimine complex or complexes with ascorbate as a ligand or ligands.

Ring-shaped rhenium(I) multinuclear complexes: improved synthesis and photoinduced multielectron accumulation.

We successfully developed selective synthesis of strongly emissive ring-shaped Re(I) multinuclear complexes (RnP(x)(n+) in Chart 1) with much higher yields compared with the previously reported method. This improved method could also be employed to prepare a novel ring-shaped multinuclear complex composed of structurally different Re(I) units. Each Re unit in RnP(x)(n+) could electrochemically accept one electron, and the multielectron reduced states of RnP(x)(n+) were stable. In the presence of triethanolamine, the ring-shaped tetranuclear and hexanuclear complexes can be photochemically reduced and accumulate 2.9-3.6 and 4.4 electrons in one molecule, respectively.

Red-light-driven photocatalytic reduction of CO2 using Os(II)-Re(I) supramolecular complexes.

The novel supramolecular complexes, which are composed of an [Os(5dmb)2(BL)](2+)-type complex (5dmb = 5,5'-dimethyl-2,2'-bipyridine; BL = 1,2-bis(4'-methyl-[2,2'-bipyridin]-4-yl)ethane) as a photosensitizer and cis,trans-[Re(BL)(CO)2{P(p-X-C6H4)3}2](+)-type complexes (X = F, Cl) as a catalyst, have been synthesized. They photocatalyzed selective reduction of CO2 to CO under red-light irradiation (λ > 620 nm). The photocatalytic abilities were affected by the phosphine ligands on the Re unit, and the supramolecule with P(p-Cl-C6H4)3 ligands exhibited better photocatalysis (ΦCO = 0.12, TONCO = 1138, TOFCO = 3.3 min(-1)). The detailed studies clarified the electron balance and material balance; i.e., one molecule of the sacrificial electron donor (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH)) donated two electrons, one molecule of CO2 accepted the two electrons, and another CO2 molecule served as an "O(2-)" acceptor to give each molecule of the two-electron oxidized compound of BIH, CO, and HCO3(-).

CO2 capture by a rhenium(I) complex with the aid of triethanolamine.

A rhenium(I) tricarbonyl diimine complex with a N,N-dimethylformamide ligand captures one CO2 molecule in the presence of triethanolamine (TEOA), giving fac-[Re(I)(bpy)(CO)3{R2N-CH2CH2O-COO}] (bpy = 2,2'-bipyridine, R = CH2CH2OH). This could be a predominant complex in various photocatalytic CO2 reduction reactions using [Re(I)(N^N)(CO)3X](n+) (N^N = diimine ligand; X = monodentate ligand; n = 0, 1) type complexes in the presence of TEOA.

Ring-shaped Re(I) multinuclear complexes with unique photofunctional properties.

We synthesized for the first time a series of emissive ring-shaped Re(I) complexes (Re-rings) with various numbers of Re(I) units and various lengths of bridge ligands. The photophysical properties of the Re-rings could be varied widely through changes in the size of the central cavity. A smaller central cavity of the Re-rings induced intramolecular π-π interactions between the ligands and consequently caused a stronger emission and a longer lifetime of the excited state. The Re-rings can function as efficient and durable photosensitizers. The combination of a trinuclear Re-ring photosensitizer with fac-[Re(bpy)(CO)3(MeCN)](+) (bpy = 2,2'-bipyridine) as a catalyst photocatalyzed CO2 reduction with the highest quantum yield of 82%.

Photocatalytic CO2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes.

Previously undescribed supramolecules constructed with various ratios of two kinds of Ru(II) complexes-a photosensitizer and a catalyst-were synthesized. These complexes can photocatalyze the reduction of CO(2) to formic acid with high selectivity and durability using a wide range of wavelengths of visible light and NADH model compounds as electron donors in a mixed solution of dimethylformamide-triethanolamine. Using a higher ratio of the photosensitizer unit to the catalyst unit led to a higher yield of formic acid. In particular, of the reported photocatalysts, a trinuclear complex with two photosensitizer units and one catalyst unit photocatalyzed CO(2) reduction (Φ(HCOOH) = 0.061, TON(HCOOH) = 671) with the fastest reaction rate (TOF(HCOOH) = 11.6 min(-1)). On the other hand, photocatalyses of a mixed system containing two kinds of model mononuclear Ru(II) complexes, and supramolecules with a higher ratio of the catalyst unit were much less efficient, and black oligomers and polymers were produced from the Ru complexes during photocatalytic reactions, which reduced the yield of formic acid. The photocatalytic formation of formic acid using the supramolecules described herein proceeds via two sequential processes: the photochemical reduction of the photosensitizer unit by NADH model compounds and intramolecular electron transfer to the catalyst unit.

Development of highly efficient supramolecular CO2 reduction photocatalysts with high turnover frequency and durability.

New Ru(II)-Re(I) supramolecular photocatalysts with a rhenium(I) biscarbonyl complex as a catalyst unit were synthesized. They photocatalyzed CO2 reduction to CO using a wide-range of visible light, and their photocatalytic abilities were strongly affected by the phosphorus ligands on the Re site. Especially, Ru-Re(FPh), with two P(p-FPh)3 ligands, exhibited tremendous photocatalytic properties, i.e. TN(CO) = 207 and phi(CO) = 0.15, and, in addition, this is one of the fastest-operating photocatalysts for CO2 reduction to CO, with TF(CO) = 281 h(-1). We also clarified a balance of transferred electrons in this photocatalytic reaction and found that the two electrons necessary for CO formation were provided by two sequential reductive quenching processes of the excited Ru photosensitizer unit by the reductant BNAH.

Dual emission from rhenium(I) complexes induced by an interligand aromatic interaction.

A series of rhenium(I) diimine complexes cis,trans-[Re(dmb)(CO)(2)(PR(1)R(2)R(3))(PR(4)R(5)R(6))](+) (dmb=4,4'-dimethyl-2,2'-bipyridine, R(n)=phenyl or alkyl), each of which bears two phosphine ligands with various numbers of phenyl groups, has been synthesized by using the photochemical ligand-substitution reaction. Detailed studies of the structural features, not only in the crystal but also in solution, indicate that the number of phenyl groups is a crucial factor in controlling the rotational conformation of the phosphine ligands, which in turn determines the extent of the π-π interaction between the aromatic diimine ligand and the phenyl group(s). The π-π interaction strongly affected both electrochemical and photophysical properties: 1) the oxidation power of the Re complex became stronger, 2) the lifetime of the excited state became longer, and 3) the Stokes shift between the (1) MLCT absorption band and emission from the corresponding (3) MLCT excited state became smaller. In particular, the diphenyl and triphenyl phosphine had much greater influence on the properties than the monophenyl phosphine ligand. Dual emission was observed from the different rotational conformers of the complexes with an intermediate number of phenyl groups in the phosphine ligands.

Development of an efficient and durable photocatalytic system for hydride reduction of an NAD(P)+ model compound using a ruthenium(II) complex based on mechanistic studies.

The mechanism of photocatalytic reduction of 1-benzylnicotinamidium cation (BNA(+)) to the 1,4-dihydro form (1,4-BNAH) using [Ru(tpy)(bpy)(L)](2+) (Ru-L(2+), where tpy = 2,2':6',2''-terpyridine, bpy = 2,2'-bipyridine, and L = pyridine and MeCN) as a photocatalyst and NEt(3) as a reductant has been clarified. On the basis of this mechanistic study, an efficient and durable photocatalytic system for selective hydride reduction of an NAD(P)(+) model compound has been developed. The photocatalytic reaction is initiated by the formation of [Ru(tpy)(bpy)(NEt(3))](2+) (Ru-NEt(3)(2+)) via the photochemical ligand substitution of Ru-L(2+). For this reason, the production rate of 1,4-BNAH using [Ru(tpy)(bpy)(MeCN)](2+) (Ru-MeCN(2+)) as a photocatalyst, from which the quantum yield of photoelimination of the MeCN ligand is greater than that of the pyridine ligand from [Ru(tpy)(bpy)(pyridine)](2+) (Ru-py(2+)), was faster than that using Ru-py(2+), especially in the first stage of the photocatalytic reduction. The photoexcitation of Ru-NEt(3)(2+) yields [Ru(tpy)(bpy)H](+) (Ru-H(+)), which reacts with BNA(+) to give 1:1 adduct [Ru(tpy)(bpy)(1,4-BNAH)](2+) (Ru-BNAH(2+)). In the presence of excess NEt(3) in the reaction solution, a deprotonation of the carbamoyl group in Ru-BNAH(2+) proceeds rapidly, mainly forming [Ru(tpy)(bpy)(1,4-BNAH-H(+))](+) (Ru-(BNAH-H(+))(+)). Although photocleavage of the adduct yields 1,4-BNAH and the cycle is completed by the re-coordination of a NEt(3) molecule to the Ru(II) center, this process competes with hydride abstraction from Ru-(BNAH-H(+))(+) by BNA(+) giving 1,4-BNAH and [Ru(tpy)(bpy)(BNA(+)-H(+))](2+). This adduct was observed as the major complex in the reaction solution after the photocatalysis was depressed and is a dead-end product because of its stability. Based on the information about the reaction mechanism and the deactivation process, we have successfully developed a new photocatalytic system using Ru-MeCN(2+) with 2 M of NEt(3) as a reductant, which could reduce more than 59 equivalent amounts of an NAD(P)(+) model, 1-benzyl-N,N-diethylnicotinamidium cation, selectively to the corresponding 1,4-dihydro form in a 6 x 10(-4) quantum yield using 436-nm light.