Bioinspired Supercharging of Photoredox Catalysis for Applications in Energy and Chemical Manufacturing

Accounts of Chemical Research, Год журнала: 2022, Номер 55(10), С. 1423 - 1434

Опубликована: Апрель 26, 2022

ConspectusFor more than a decade, photoredox catalysis has been demonstrating that when photoactive catalysts are irradiated with visible light, reactions occur under milder, cheaper, and environmentally friendlier conditions. Furthermore, this methodology allows for the activation of abundant chemicals into valuable products through novel mechanisms otherwise inaccessible. The approach, however, primarily used pharmaceutical applications, where its implementation highly effective, but typically rudimentary understanding involved in these transformations. From global perspective, manufacture everyday by chemical industry as whole currently accounts 10% total energy consumption generates 7% world's greenhouse gases annually. In context, Bio-Inspired Light-Escalated Chemistry (BioLEC) Energy Frontier Research Center (EFRC) was founded to supercharge approach applications manufacturing aimed at reducing emissions burden, using bioinspired schemes harvest multiple electrons drive endothermically uphill reactions. comprises diverse group researchers expertise includes synthetic chemistry, biophysics, physical engineering. team works together gain deeper mechanistic details while amplifying light-driven methodologies.In Account, we review some major advances understanding, applicability made possible collaborative Center. Combining sophisticated spectroscopic tools photophysics tactics enhanced led development techniques reactivities greatly expand field capabilities. Account is intended highlight how interplay between disciplines can have impact facilitate advance field. For example, such time-resolved dielectric loss (TRDL) pulse radiolysis providing insights not previously available. Hypothesis-driven photocatalyst design thus broadening scope several existing Moreover, bioconjugation approaches triplet–triplet annihilation created new avenues exploration reactivities. Lastly, our multidisciplinary tackling real-world problems inspired efficient methods depolymerization lignin artificial polymers.

Язык: Английский

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Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(20), С. 11402 - 11414

Опубликована: Май 15, 2023

Sensitized triplet–triplet annihilation upconversion is a promising strategy to use visible light for chemical reactions requiring the energy input of UV photons. This avoids unsafe ultraviolet sources and can mitigate photo-damage provide access reactions, which filter effects hamper direct excitation. Here, we report new approach make blue-to-UV more amenable photochemical applications. The tethering naphthalene unit cyclometalated iridium(III) complex yields bichromophore with high triplet (2.68 eV) naphthalene-based reservoir featuring lifetime 72.1 μs, roughly factor 20 longer than photoactive excited state parent complex. In combination three different annihilators, consistently lower thresholds crossover from quadratic into linear excitation power dependence regime were observed compared system composed 2,5-diphenyloxazole annihilator sufficiently robust under long-term blue irradiation continuously high-energy singlet-excited that drive normally light. Both photoredox transfer catalyses feasible using this concept, including reductive N–O bond cleavage Weinreb amides, C–C coupling reaction based on aryl debromination, two Paternò–Büchi [2 + 2] cycloaddition reactions. Our work seems relevant in context developing strategies driving energetically demanding photochemistry low-energy

Язык: Английский

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First‐Row d⁶ Metal Complex Enables Photon Upconversion and Initiates Blue Light‐Dependent Polymerization with Red Light

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(43)

Опубликована: Сен. 8, 2023

Photosensitizers for sensitized triplet-triplet annihilation upconversion (sTTA-UC) often rely on precious heavy metals, whereas coordination complexes based abundant first-row transition metals are less common. This is mainly because long-lived triplet excited states more difficult to obtain 3d particularly when the d-subshell only partially filled. Here, we report first example of sTTA-UC a 3d6 metal photosensitizer yielding an performance competitive with metal-based analogues. Using newly developed Cr0 featuring equally good photophysical properties as OsII benchmark complex in combination acetylene-decorated anthracene annihilator, red-to-blue achievable. The efficiency under optimized conditions 1.8 %, and excitation power density threshold reach strong limit 5.9 W/cm2 . These factors, along high photostability, permit initiation acrylamide polymerization by red light, radiative energy transfer between delayed annihilator fluorescence blue light absorbing photo-initiator. Our study provides proof-of-concept photon elusive analogues widely employed d6 photosensitizers, their application photochemical reactions triggered wavelengths close near-infrared.

Язык: Английский

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Red-Shifting Blue Light Photoredox Catalysis for Organic Synthesis: A Graphical Review

SynOpen, Год журнала: 2023, Номер 07(01), С. 76 - 87

Опубликована: Фев. 1, 2023

Abstract Photoredox catalysis has revolutionized synthetic chemistry in recent decades. However, the field traditionally used high-energy blue/ultraviolet light to activate chromophores. High-energy irradiation is associated with several drawbacks (e.g., activation of sensitive functional groups, undesired metal-ligand homolysis, background molecules, and poor penetration), which led researchers develop alternative systems lower energy deep red (DR) or near-infrared (NIR) light. This graphical review provides a concise overview photophysical principles relevant photoredox catalysis. Several applications that benefit from low-energy irradiation, such as large-scale batch reactions, photodynamic therapy, biological labeling, multi-photon excitation are reviewed.

Язык: Английский

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Steric and Electronic Influence of Excited-State Decay in Cu(I) MLCT Chromophores

Accounts of Chemical Research, Год журнала: 2024, Номер 57(19), С. 2872 - 2886

Опубликована: Сен. 11, 2024

ConspectusFor the past 11 years, a dedicated effort in our research group focused on fundamentally advancing photophysical properties of cuprous

Язык: Английский

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