Photocatalytic Regeneration of a Nicotinamide Adenine Nucleotide Mimic with Water-Soluble Iridium(III) Complexes.

Nicotinamide adenine nucleotide (NADH) is involved in many biologically relevant redox reactions, and the photochemical regeneration of its oxidized form (NAD+) under physiological conditions is of interest for combined photo- and biocatalysis. Here, we demonstrate that tri-anionic, water-soluble variants of typically very lipophilic iridium(III) complexes can photo-catalyze the reduction of an NAD+ mimic in a comparatively efficient manner. In combination with a well-known rhodium co-catalyst to facilitate regioselective reactions, these iridium(III) photo-reductants outcompete the commonly used [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) photosensitizer in water by up to 1 order of magnitude in turnover frequency. This improved reactivity is attributable to the strong excited-state electron donor properties and the good chemical robustness of the tri-anionic iridium(III) sensitizers, combined with their favorable Coulombic interaction with the di-cationic rhodium co-catalyst. Our findings seem relevant in the greater context of photobiocatalysis, for which access to strong, efficient, and robust photoreductants with good water solubility can be essential.

Water-Soluble Tris(cyclometalated) Iridium(III) Complexes for Aqueous Electron and Energy Transfer Photochemistry.

Cyclometalated iridium(III) complexes are frequently employed in organic light emitting diodes, and they are popular photocatalysts for solar energy conversion and synthetic organic chemistry. They luminesce from redox-active excited states that can have high triplet energies and long lifetimes, making them well suited for energy transfer and photoredox catalysis. Homoleptic tris(cyclometalated) iridium(III) complexes are typically very hydrophobic and do not dissolve well in polar solvents, somewhat limiting their application scope. We developed a family of water-soluble sulfonate-decorated variants with tailored redox potentials and excited-state energies to address several key challenges in aqueous photochemistry.First, we aimed at combining enzyme with photoredox catalysis to synthesize enantioenriched products in a cyclic reaction network. Since the employed biocatalyst operates best in aqueous solution, a water-soluble photocatalyst was needed. A new tris(cyclometalated) iridium(III) complex provided enough reducing power for the photochemical reduction of imines to racemic mixtures of amines and furthermore was compatible with monoamine oxidase (MAO-N-9), which deracemized this mixture through a kinetic resolution of the racemic amine via oxidation to the corresponding imine. This process led to the accumulation of the unreactive amine enantiomer over time. In subsequent studies, we discovered that the same iridium(III) complex photoionizes under intense irradiation to give hydrated electrons as a result of consecutive two-photon excitation. With visible light as energy input, hydrated electrons become available in a catalytic fashion, thereby allowing the comparatively mild reduction of substrates that would typically only be reactive under harsher conditions. Finally, we became interested in photochemical upconversion in aqueous solution, for which it was desirable to obtain water-soluble iridium(III) compounds with very high triplet excited-state energies. This goal was achieved through improved ligand design and ultimately enabled sensitized triplet-triplet annihilation upconversion unusually far into the ultraviolet spectral range.Studies of photoredox catalysis, energy transfer catalysis, and photochemical upconversion typically rely on the use of organic solvents. Water could potentially be an attractive alternative in many cases, but photocatalyst development lags somewhat behind for aqueous solution compared to organic solvent. The purpose of this Account is to provide an overview of the breadth of new research perspectives that emerged from the development of water-soluble fac-[Ir(ppy)]3 complexes (ppy = 2-phenylpyridine) with sulfonated ligands. We hope to inspire the use of some of these or related coordination compounds in aqueous photochemistry and to stimulate further conceptual developments at the interfaces of coordination chemistry, photophysics, biocatalysis, and sustainable chemistry.

UV Light Generation and Challenging Photoreactions Enabled by Upconversion in Water.

Sensitized triplet-triplet annihilation (sTTA) is the most promising mechanism for pooling the energy of two visible photons, but its applications in solution were so far limited to organic solvents, with a current maximum of the excited-singlet state energy of 3.6 eV. By combining tailor-made iridium complexes with naphthalenes, we demonstrate blue-light driven upconversion in water with unprecedented singlet-state energies approaching 4 eV. The annihilators have outstanding excited-state reactivities enabling challenging photoreductions driven by sTTA. Specifically, we found that an aryl-bromide bond activation can be achieved with blue photons, and we obtained full conversion for the very energy-demanding decomposition of a persistent ammonium compound as typical water pollutant, not only with a cw laser but also with an LED light source. These results provide the first proof-of-concept for the usage of low-power light sources for challenging reactions employing blue-to-UV upconversion in water and pave the way for the further development of sustainable light-harvesting applications.

Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins.

Many photoactive metal complexes can act as electron donors or acceptors upon photoexcitation, but hydrogen atom transfer (HAT) reactivity is rare. We discovered that a typical representative of a widely used class of iridium hydride complexes acts as an H-atom donor to unactivated olefins upon irradiation at 470 nm in the presence of tertiary alkyl amines as sacrificial electron and proton sources. The catalytic hydrogenation of simple olefins served as a test ground to establish this new photo-reactivity of iridium hydrides. Substrates that are very difficult to activate by photoinduced electron transfer were readily hydrogenated, and structure-reactivity relationships established with 12 different olefins are in line with typical HAT reactivity, reflecting the relative stabilities of radical intermediates formed by HAT. Radical clock, H/D isotope labeling, and transient absorption experiments provide further mechanistic insight and corroborate the interpretation of the overall reactivity in terms of photo-triggered hydrogen atom transfer (photo-HAT). The catalytically active species is identified as an Ir(ii) hydride with an IrII-H bond dissociation free energy around 44 kcal mol-1, which is formed after reductive 3MLCT excited-state quenching of the corresponding Ir(iii) hydride, i.e. the actual HAT step occurs on the ground-state potential energy surface. The photo-HAT reactivity presented here represents a conceptually novel approach to photocatalysis with metal complexes, which is fundamentally different from the many prior studies relying on photoinduced electron transfer.

Enantioselective synthesis of amines by combining photoredox and enzymatic catalysis in a cyclic reaction network.

Visible light-driven reduction of imines to enantioenriched amines in aqueous solution is demonstrated for the first time. Excitation of a new water-soluble variant of the widely used [Ir(ppy)3] (ppy = 2-phenylpyridine) photosensitizer in the presence of a cyclic imine affords a highly reactive α-amino alkyl radical that is intercepted by hydrogen atom transfer (HAT) from ascorbate or thiol donors to afford the corresponding amine. The enzyme monoamine oxidase (MAO-N-9) selectively catalyzes the oxidation of one of the enantiomers to the corresponding imine. Upon combining the photoredox and biocatalytic processes under continuous photo-irradiation, enantioenriched amines are obtained in excellent yields. To the best of our knowledge, this is the first demonstration of a concurrent photoredox- and enzymatic catalysis leading to a light-driven asymmetric synthesis of amines.