☆ 4.6 Review

Recent Advances in Metal-Based Molecular Photosensitizers for Artificial Photosynthesis

CATALYSTS (2022)

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Bioinspired Artificial Photosynthetic Systems

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Summary: This article presents recent advances in developing artificial photosynthetic systems, including photobioelectrochemical cells interfacing with electrodes, light-induced electron transfer, and integration of artificial photosynthetic modules into dynamic nucleic acid networks.

CHEMISTRY-A EUROPEAN JOURNAL (2022)

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Review Chemistry, Inorganic & Nuclear

Luminescent chromium(0) and manganese(i) complexes

Christina Wegeberg et al.

Summary: This article highlights recently discovered chromium(0) and manganese(i) complexes emitting from metal-to-ligand charge transfer excited states, with MLCT lifetimes in the nanosecond regime. Although luminescence quantum yields are comparatively low, the photophysical properties provide insight for the further development of new luminescent first-row transition metal complexes.

DALTON TRANSACTIONS (2022)

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Review Chemistry, Multidisciplinary

Porphyrin-based heterogeneous photocatalysts for solar energy conversion

Yuheng Zhang et al.

Summary: This article reviews the research progress in the design of porphyrin molecules in the field of heterogeneous photocatalysis in recent years. The application of interface control and spatial confinement effect in porphyrin-based hybrid photocatalysts is also introduced. The future development direction and main challenges in the research of porphyrin-based photocatalysts are discussed.

CHINESE CHEMICAL LETTERS (2022)

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Article Chemistry, Multidisciplinary

Recent progresses in molecular-based artificial photosynthesis

Fausto Puntoriero et al.

Summary: Bio-inspired artificial photosynthesis aims to produce high-energy content chemicals using solar energy and molecular components. Recent results show the use of suitable arrangements to obtain efficient catalysts for water oxidation, the use of aromatics as bridging ligands for CO2 reduction, and the use of earth-abundant metal complexes as photosensitizers.

CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY (2022)

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Review Chemistry, Applied

Mini review on the molecular engineering of photosensitizer: Current status and prospects of metal-free/porphyrin frameworks at the interface of dye-sensitized solar cells

Selvam Ramasamy et al.

Summary: This mini-review provides an overview of materials based on donor-linker-acceptor structural motifs and summarizes the current state of research, offering insights for the design of new, effective photovoltaic materials. The article focuses on the current development in designing porphyrin dyes for use in dye-sensitized solar cells (DSSCs) and highlights effective molecular strategies for developing efficient porphyrin dyes. Additionally, recent advancements in DSSCs using metal-free organic-sensitizers at the interface are discussed.

DYES AND PIGMENTS (2022)

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Review Chemistry, Inorganic & Nuclear

Photofunctional molecular assembly for artificial photosynthesis: Beyond a simple dye sensitization strategy

Atsushi Kobayashi et al.

Summary: This review focuses on the photofunctional molecular assemblies on the surfaces of rigid semiconductors or soft lipid membranes to overcome backward reactions in Z-scheme water-splitting photocatalysis. Approaches based on the dye-sensitization mechanism can improve photoinduced charge-separation efficiency and regulate the reaction field and pathway in photocatalytic O-2 and H-2 evolution reactions, providing powerful techniques for improving photocatalytic activity.

COORDINATION CHEMISTRY REVIEWS (2022)

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Review Chemistry, Inorganic & Nuclear

Aluminum(III) porphyrin: A unique building block for artificial photosynthetic systems

Niloofar Zarrabi et al.

Summary: Despite being the most abundant metal on Earth, aluminum(III) metal ion centered porphyrin derivatives have received less attention compared to transition metal porphyrin derivatives. AlPor possesses unique dual bonding features and rich redox chemistry and optical properties, making it a valuable building block for constructing donor-acceptor systems for various applications. These systems can mimic natural photosynthesis and develop artificial photosynthetic systems for solar energy utilization.

COORDINATION CHEMISTRY REVIEWS (2021)

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Article Chemistry, Inorganic & Nuclear

Living Long and Prosperous: Productive Intraligand Charge-Transfer States from a Rhenium(I) Terpyridine Photosensitizer with Enhanced Light Absorption

Ricardo Fernandez-Teran et al.

Summary: The ground- and excited-state properties of six rhenium(I)kappa N-2-tricarbonyl complexes with 4'-(4-substituted-phenyl)-terpyridine ligands bearing substituents of different electron-donating abilities were evaluated. Significant changes in electrochemical potentials and triplet metal-to-ligand charge-transfer lifetimes were observed, with the most electron-donating group leading to the appearance of a strong absorption band and a dramatic enhancement of the excited-state lifetime. The dynamics and character of the excited states were assigned using a combination of techniques, and selected complexes showed promising results as photosensitizers for hydrogen production.

INORGANIC CHEMISTRY (2021)

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Article Chemistry, Multidisciplinary

Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation

T. Gamze Ulusoy Ghobadi et al.

Summary: The study successfully constructed a stable iron-sensitized photoanode with exceptional photosensitizing ability and connectivity to cobalt water oxidation catalytic sites via cyanide linkers. This breakthrough in chromophore-catalyst assemblies will inspire interest in dye-sensitization with robust bulk systems for photoconversion applications.

CHEMISTRY-A EUROPEAN JOURNAL (2021)

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Article Chemistry, Multidisciplinary

Fundamental Characterization, Photophysics and Photocatalysis of a Base Metal Iron(II)-Cobalt(III) Dyad

Marina Huber-Gedert et al.

Summary: A novel iron-cobalt dyad has been obtained and extensively characterized, showing high stability and excited-state landscape in solution. The attachment of cobaloxime to the iron photosensitizer increases the activity of the catalyst, potentially making it more effective in photocatalytic proton reduction experiments. This work sheds new light on the functionality of base metal dyads for future, more efficient and sustainable proton reduction systems.

CHEMISTRY-A EUROPEAN JOURNAL (2021)

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Article Chemistry, Inorganic & Nuclear

Next Generation Cuprous Phenanthroline MLCT Photosensitizer Featuring Cyclohexyl Substituents

Michael C. Rosko et al.

Summary: The newly synthesized Cu(I) photosensitizer exhibits excellent performance in terms of molecular photophysics, electrochemistry, and electronic structure, even when dissolved in Lewis basic solvents. It shows impressive optical parameters and stability.

INORGANIC CHEMISTRY (2021)

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Article Chemistry, Multidisciplinary

Manganese(i) complexes with metal-to-ligand charge transfer luminescence and photoreactivity

Patrick Herr et al.

Summary: Metal complexes with d(6) valence electron configuration often exhibit luminescent metal-to-ligand charge transfer (MLCT) excited states, useful for various applications. Iron(ii) has been suggested as an Earth-abundant alternative, but no iron(ii) complex has been reported to show MLCT emission. In this study, manganese(I) complexes with isocyanide chelate ligands were found to exhibit MLCT luminescence in solution at room temperature, showing promising applications in energy and electron transfer reactions.

NATURE CHEMISTRY (2021)

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Article Chemistry, Multidisciplinary

Development of a panchromatic photosensitizer and its application to photocatalytic CO2 reduction

Mari Irikura et al.

Summary: The heteroleptic osmium(ii) complex demonstrated the ability to absorb the full wavelength range of visible light and function as a panchromatic redox photosensitizer. It was able to catalyze the reduction of CO2 to HCOOH under light irradiation, showcasing its potential for diverse photocatalytic applications.

CHEMICAL SCIENCE (2021)

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Article Chemistry, Inorganic & Nuclear

β-Diketiminate-supported iridium photosensitizers with increased excited-state reducing power

Jong-Hwa Shon et al.

Summary: A series of bis-cyclometalated iridium complexes have been prepared, utilizing triazole or NHC-based cyclometalating ligands with substituted beta-diketiminate (NacNac) ancillary ligands. The results show that the new iridium complexes exhibit stronger excited-state reduction potentials, making them the most potent visible-light iridium photoreductants reported to date. These photoreductants are capable of activating challenging organohalide substrates, although with modest conversion rates.

INORGANIC CHEMISTRY FRONTIERS (2021)

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Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers

Jong-Hwa Shon et al.

Summary: This study demonstrates that strong bis-cyclometalated iridium photoreductants with specific ligands can achieve high-yielding photoredox transformations of challenging substrates with very simple reaction conditions requiring only a single sacrificial reagent.

CHEMICAL SCIENCE (2021)

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Article Chemistry, Physical

Structure and excited-state dynamics of dimeric copper(i) photosensitizers investigated by time-resolved X-ray and optical transient absorption spectroscopy

Lucia Velasco et al.

Summary: Time-resolved X-ray and optical transient absorption spectroscopy were combined with DFT and XANES calculations to study the photoexcitation dynamics of three homoleptic Cu(i) dimeric chromophores. Results showed distinct excited state lifetimes for different complexes, which were attributed to solvent effects and ligand flexibility upon copper flattening. These findings are important for understanding the structural dynamics of Cu-based compounds and their potential integration into solar energy conversion systems.

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Photosensitizers for H2 Evolution Based on Charged or Neutral Zn and Sn Porphyrins

Emmanouil Giannoudis et al.

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Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

Kristjan Kunnus et al.

NATURE COMMUNICATIONS (2020)

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High-Redox-Potential Chromophores for Visible-Light-Driven Water Oxidation at Low pH

Lei Wang et al.

ACS CATALYSIS (2020)

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Yield-not only Lifetime-of the Photoinduced Charge-Separated State in Iridium Complex-Polyoxometalate Dyads Impact Their Hydrogen Evolution Reactivity

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Shedding Light on the Molecular Surface Assembly at the Nanoscale Level: Dynamics of a Re(I) Carbonyl Photosensitizer with a Coadsorbed Cobalt Tetrapyridyl Water Reduction Catalyst on ZrO2

Kerstin Oppelt et al.

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Ping Wang et al.

NATIONAL SCIENCE REVIEW (2020)

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A bright future for photosensitizers

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Role of MLCT States in the Franck-Condon Region of Neutral, Heteroleptic Cu(I)-4H-imidazolate Complexes: A Spectroscopic and Theoretical Study

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Intersystem Crossing and Triplet Dynamics in an Iron(II) N-Heterocyclic Carbene Photosensitizer

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Surface immobilized copper(I) diimine photosensitizers as molecular probes for elucidating the effects of confinement at interfaces for solar energy conversion

Michael S. Eberhart et al.

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Organic linkage controls the photophysical properties of covalent photosensitizer-polyoxometalate hydrogen evolution dyads

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Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer

Raphael M. Jay et al.

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Development of Visible-Light Driven Cu(I) Complex Photosensitizers for Photocatalytic CO2 Reduction

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Gautam D. Stroscio et al.

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Watching Intermolecular Light-Induced Charge Accumulation on Naphthalene Diimide by Tris(bipyridyl)ruthenium(II) Photosensitizer

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Remarkably long-lived excited states of copper photosensitizers containing an extended π-system based on an anthracene moiety

Robin Giereth et al.

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Excited-state dynamics of heteroleptic copper(i) photosensitizers and their electrochemically reduced forms containing a dipyridophenazine moiety - a spectroelectrochemical transient absorption study

Ying Zhang et al.

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Peter Zimmer et al.

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Enhancing the Visible-Light Absorption and Excited-State Properties of Cu(I) MLCT Excited States

Sofia Garakyaraghi et al.

INORGANIC CHEMISTRY (2018)

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Mimicking the Key Functions of Photosystem II in Artificial Photosynthesis for Photoelectrocatalytic Water Splitting

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An artificial photosynthetic system for photoaccumulation of two electrons on a fused dipyridophenazine (dppz)-pyridoquinolinone ligand

Jean-Francois Lefebvre et al.

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Visible Light-Activated CO Release and O-1(2) Photosensitizer Formation with Ru(II),Mn(I) Complexes

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

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Heteroleptic Copper Photosensitizers: Why an Extended π-System Does Not Automatically Lead to Enhanced Hydrogen Production

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CHEMISTRY-A EUROPEAN JOURNAL (2017)

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N-Heterocyclic Carbene Complexes of Iron as Photosensitizers for Light-Induced Water Reduction

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Electron Accumulation on Naphthalene Diimide Photosensitized by [Ru(2,2'-Bipyridine)3]2+

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Potent Bis-Cyclometalated Iridium Photoreductants with β-Diketiminate Ancillary Ligands

Jong-Hwa Shon et al.

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

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Copper Photosensitizers Containing P∧N Ligands and Their Influence on Photoactivity and Stability

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Synthesis, structure, and excited state kinetics of heteroleptic Cu(I) complexes with a new sterically demanding phenanthroline ligand

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Photocatalytic CO2 Reduction Using Cu(I) Photosensitizers with a Fe(II) Catalyst

Hiroyuki Takeda et al.

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Integration of Artificial Photosynthesis System for Enhanced Electronic Energy-Transfer Efficacy: A Case Study for Solar-Energy Driven Bioconversion of Carbon Dioxide to Methanol

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Rhenium(I) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction

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Rate and Stability of Photocatalytic Water Oxidation using [Ru(bpy)3]2+ as Photosensitizer

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ACS CATALYSIS (2016)

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Determination of side products in the photocatalytic generation of hydrogen with copper photosensitizers by resonance Raman spectroelectrochemistry

Ying Zhang et al.

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Visible-Light-Driven Water Oxidation on a Photoanode by Supramolecular Assembly of Photosensitizer and Catalyst

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Evaluation of Chromophore and Assembly Design in Light-Driven Water Splitting with a Molecular Water Oxidation Catalyst

Matthew V. Sheridan et al.

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The emergence of copper(I)-based dye sensitized solar cells

Catherine E. Housecroft et al.

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Interplays of excited state structures and dynamics in copper(I) diimine complexes: Implications and perspectives

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Platinum(II)-porphyrin as a sensitizer for visible-light driven water oxidation in neutral phosphate buffer

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An Iron-Based Photosensitizer with Extended Excited-State Lifetime: Photophysical and Photovoltaic Properties

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Visible Light-Driven Water Oxidation Promoted by Host-Guest Interaction between Photosensitizer and Catalyst with A High Quantum Efficiency

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