Photoredox catalysis has been prominent in many applications, including solar fuels, organic synthesis, and polymer chemistry. Photocatalytic activity directly depends on the photophysical and electrochemical properties of photocatalysts in both the ground state and excited state. Controlling those properties, therefore, is imperative to achieve the desired photocatalytic activity. Redox potential is one important factor that impacts both the thermodynamic and kinetic aspects of key elementary steps in photoredox catalysis. In many challenging reactions in organic synthesis, high redox potentials of the substrates hamper the reaction, leading to slow conversion. Thus, the development of photocatalysts with extreme redox potentials, accompanied by potent reducing or oxidizing power, is required to execute high-yielding thermodynamically demanding reactions. In this review, we will introduce strategies for accessing extreme redox potentials in photocatalytic transformations. These include molecular design strategies for preparing photosensitizers that are exceptionally strong ground-state or excited-state reductants or oxidants, highlighting both organic and metal-based photosensitizers. We also outline methodological approaches for accessing extreme redox potentials, using two-photon activation, or combined electrochemical/photochemical strategies to generate potent redox reagents from precursors that have milder potentials.
more »
« less
Photophysical Properties and Redox Potentials of Photosensitizers for Organic Photoredox Transformations
Abstract Photoredox catalysis has proven to be a powerful tool in synthetic organic chemistry. The rational design of photosensitizers with improved photocatalytic performance constitutes a major advancement in photoredox organic transformations. This review summarizes the fundamental ground-state and excited-state photophysical and electrochemical attributes of molecular photosensitizers, which are important determinants of their photocatalytic reactivity.
more »
« less
- Award ID(s):
- 1846831
- NSF-PAR ID:
- 10317925
- Date Published:
- Journal Name:
- Synlett
- ISSN:
- 0936-5214
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract Metal‐halide perovskites have been explored as photocatalysts for CO2reduction. We report that perovskite photocatalytic CO2reduction in organic solvents is likely problematic. Instead, the detected products (i.e., CO) likely result from a photoredox organic transformation involving the solvent. Our observations have been validated using isotopic labeling experiments, band energy analysis, and new control experiments. We designed a typical perovskite photocatalytic setup in organic solvents that led to CO production of up to ≈1000 μmol g−1 h−1. CO2reduction in organic solvents must be studied with extra care because photoredox organic transformations can produce orders of magnitude higher rate of CO or CH4than is typical for CO2reduction routes. Though CO2reduction is not likely to occur, in situ CO generation is extremely fast. Hence a suitable system can be established for challenging organic reactions that use CO as a feedstock but exploit the solvent as a CO surrogate.
-
more » « less
Abstract Metal‐halide perovskites have been explored as photocatalysts for CO2reduction. We report that perovskite photocatalytic CO2reduction in organic solvents is likely problematic. Instead, the detected products (i.e., CO) likely result from a photoredox organic transformation involving the solvent. Our observations have been validated using isotopic labeling experiments, band energy analysis, and new control experiments. We designed a typical perovskite photocatalytic setup in organic solvents that led to CO production of up to ≈1000 μmol g−1 h−1. CO2reduction in organic solvents must be studied with extra care because photoredox organic transformations can produce orders of magnitude higher rate of CO or CH4than is typical for CO2reduction routes. Though CO2reduction is not likely to occur, in situ CO generation is extremely fast. Hence a suitable system can be established for challenging organic reactions that use CO as a feedstock but exploit the solvent as a CO surrogate.
-
Abstract One-photon-absorbing photosensitizers are commonly used in homogeneous photocatalysis which require the absorption of ultraviolet (UV) /visible light to populate the desired excited states with adequate energy and lifetime. Nevertheless, the limited penetration depth and competing absorption by organic substrates of UV/visible light calls upon exploring the utilization of longer-wavelength irradiation, such as near-infrared light (λ irr > 700 nm). Despite being found applications in photodynamic therapy and bioimaging, two-photon absorption (TPA), the simultaneous absorption of two photons by one molecule, has been rarely explored in homogeneous photocatalysis. Herein, we report a group of ruthenium polypyridyl complexes possessing TPA capability that can drive a variety of organic transformations upon irradiation with 740 nm light. We demonstrate that these TPA ruthenium complexes can operate in an analogous manner as one-photon-absorbing photosensitizers for both energy-transfer and photoredox reactions, as well as function in concert with a transition metal co-catalyst for metallaphotoredox C–C coupling reactions.more » « less
-
Photoinduced atom transfer radical polymerization (photo-ATRP) has risen to the forefront of modern polymer chemistry as a powerful tool giving access to well-defined materials with complex architecture. However, most photo-ATRP systems can only generate radicals under biocidal UV light and are oxygen-sensitive, hindering their practical use in the synthesis of polymer biohybrids. Herein, inspired by the photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization, we demonstrate a dual photoredox/copper catalysis that allows open-air ATRP under green light irradiation. Eosin Y was used as an organic photoredox catalyst (PC) in combination with a copper complex (X–Cu II /L). The role of PC was to trigger and drive the polymerization, while X–Cu II /L acted as a deactivator, providing a well-controlled polymerization. The excited PC was oxidatively quenched by X–Cu II /L, generating Cu I /L activator and PC˙ + . The ATRP ligand (L) used in excess then reduced the PC˙ + , closing the photocatalytic cycle. The continuous reduction of X–Cu II /L back to Cu I /L by excited PC provided high oxygen tolerance. As a result, a well-controlled and rapid ATRP could proceed even in an open vessel despite continuous oxygen diffusion. This method allowed the synthesis of polymers with narrow molecular weight distributions and controlled molecular weights using Cu catalyst and PC at ppm levels in both aqueous and organic media. A detailed comparison of photo-ATRP with PET-RAFT polymerization revealed the superiority of dual photoredox/copper catalysis under biologically relevant conditions. The kinetic studies and fluorescence measurements indicated that in the absence of the X–Cu II /L complex, green light irradiation caused faster photobleaching of eosin Y, leading to inhibition of PET-RAFT polymerization. Importantly, PET-RAFT polymerizations showed significantly higher dispersity values (1.14 ≤ Đ ≤ 4.01) in contrast to photo-ATRP (1.15 ≤ Đ ≤ 1.22) under identical conditions.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1055/a-1390-9065
