Long wavelength near-infrared and red light-driven consecutive photo-induced electron transfer for highly effective photoredox catalysis DOI Creative Commons
Le Zeng, Ling Huang,

Zhi Huang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 23, 2024

Abstract Consecutive photoinduced electron transfer (conPET) processes accumulate the energies of two photons to overcome thermodynamic limit traditional photoredox catalysis. However, excitation wavelength conPET systems mainly focused on short visible light, leading photodamage and incompatibility with large-scale reactions. Herein, we report triggered by near-infrared (NIR) red light. Specifically, a blue-absorbing photocatalyst, perylene diimide (PDI) is sensitized palladium-based photosensitizer triplet excited state ( 3 PDI * ), which generates radical anion (PDI • – ) over 100-fold faster than that in conventional conPET. Accordingly, photoreduction superior reaction rate penetration depth, as well reduced detected. More importantly, our work offers comprehensive design rules for triplet-mediated strategy, whose versatility confirmed metal-free dye pairs NIR-active PtTNP/PDI. Notably, achieves NIR-driven atom polymerization using an inert aromatic halide initiator.

Language: Английский

Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis DOI
Nicholas E. S. Tay, Dan Lehnherr, Tomislav Rovis

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

Citations

357
Photon Upconversion for Photovoltaics and Photocatalysis: A Critical Review DOI
Bryce S. Richards, Damien Hudry, Dmitry Busko

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(15), P. 9165 - 9195

Published: July 30, 2021

Opportunities for enhancing solar energy harvesting using photon upconversion are reviewed. The increasing prominence of bifacial cells is an enabling factor the implementation upconversion, however, when realistic constraints current best-performing silicon devices considered, many challenges remain before photovoltaics operating under nonconcentrated sunlight can be enhanced via lanthanide-based upconversion. A photophysical model reveals that >1–2 orders magnitude increase in intermediate state lifetime, transfer rate, or generation rate would needed such could start to become efficient. Methods as use cosensitizers expand absorption range and plasmonics photonic structures opportunities these approaches (or combinations thereof) achieve efficient discussed. opportunity performance technologies luminescent concentrators by combining together with micro-optics also Triplet–triplet annihilation-based progressing steadily toward being relevant lower-bandgap cells. Looking photocatalysis, modeling indicates blue-to-ultraviolet lanthanide systems very inefficient. However, hope remains this direction organic visible-light-active photocatalysts.

Language: Английский

Citations

300
Photophysical Properties and Redox Potentials of Photosensitizers for Organic Photoredox Transformations DOI
Thomas S. Teets, Yanyu Wu, Dooyoung Kim

et al.

Synlett, Journal Year: 2021, Volume and Issue: 33(12), P. 1154 - 1179

Published: Feb. 15, 2021

Abstract Photoredox catalysis has proven to be a powerful tool in synthetic organic chemistry. The rational design of photosensitizers with improved photocatalytic performance constitutes major advancement photoredox transformations. This review summarizes the fundamental ground-state and excited-state photophysical electrochemical attributes molecular photosensitizers, which are important determinants their reactivity.

Language: Английский

Citations

115
Recent Development in Sensitizers for Lanthanide-Doped Upconversion Luminescence DOI
Xingwen Cheng, Jie Zhou,

Jingyi Yue

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(21), P. 15998 - 16050

Published: Oct. 4, 2022

The attractive features of lanthanide-doped upconversion luminescence (UCL), such as high photostability, nonphotobleaching or photoblinking, and large anti-Stokes shift, have shown great potentials in life science, information technology, energy materials. Therefore, UCL modulation is highly demanded toward expected emission wavelength, lifetime, relative intensity order to satisfy stringent requirements raised from a wide variety areas. Unfortunately, the majority efforts been devoted either simple codoping multiple activators variation hosts, while very little attention has paid critical role that sensitizers playing. In fact, different possess excitation wavelengths transfer pathways (to activators), which will lead features. Thus, rational design shall provide extra opportunities for tuning, particularly side. this review, we specifically focus on advances sensitizers, including current status, working mechanisms, principles, well future challenges endeavor directions.

Language: Английский

Citations

112
Manipulating Exciton Dynamics toward Simultaneous High-Efficiency Narrowband Electroluminescence and Photon Upconversion by a Selenium-Incorporated Multiresonance Delayed Fluorescence Emitter DOI
Xiaosong Cao,

Ke Pan,

Jingsheng Miao

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(50), P. 22976 - 22984

Published: Dec. 7, 2022

Multiresonance thermal activated delayed fluorescence (MR-TADF) materials with an efficient spin-flip transition between singlet and triplet excited states remain demanding. Herein, we report MR-TADF compound (BN-Se) simultaneously possessing (reverse) intersystem crossing (ISC/RISC), fast radiative decay, close-to-unity quantum yield, narrowband emission by embedding a single selenium atom into common 4,4'-diazaborin framework. Benefitting from the high RISC efficiency accelerated heavy-atom effect, organic light-emitting diodes (OLEDs) based on BN-Se manifest excellent performance external of up to 32.6% ultralow roll-off 1.3% at 1000 cd m-2. Furthermore, ISC small inherent energy loss also render superior photosensitizer realize first example visible (λex > 450 nm)-to-UV (λem < 350 nm) triplet-triplet annihilation upconversion, (21.4%) extremely low threshold intensity (1.3 mW cm-2). This work not only aids in designing advanced pure molecules exciton dynamics but highlights value compounds beyond OLED applications.

Language: Английский

Citations

91
Nanoengineering Triplet–Triplet Annihilation Upconversion: From Materials to Real-World Applications DOI
Tracy H. Schloemer, Pournima Narayanan, Qi Zhou

et al.

ACS Nano, Journal Year: 2023, Volume and Issue: 17(4), P. 3259 - 3288

Published: Feb. 17, 2023

Using light to control matter has captured the imagination of scientists for generations, as there is an abundance photons at our disposal. Yet delivering beyond surface many photoresponsive systems proven challenging, particularly scale, due attenuation via absorption and scattering losses. Triplet–triplet annihilation upconversion (TTA-UC), a process which allows low energy be converted high photons, poised overcome these challenges by allowing precise spatial generation its nonlinear nature. With wide range sensitizer annihilator motifs available TTA-UC, researchers seek integrate materials in solution or solid-state applications. In this Review, we discuss nanoengineering deployment strategies highlight their uses recent state-of-the-art examples TTA-UC integrated both Considering implementation tactics application-specific requirements, identify critical needs push TTA-UC-based applications from academic curiosity scalable technology.

Language: Английский

Citations

83
Recent advances in triplet–triplet annihilation upconversion and singlet fission, towards solar energy applications DOI Creative Commons
Andrew J. Carrod, Victor Gray, Karl Börjesson

et al.

Energy & Environmental Science, Journal Year: 2022, Volume and Issue: 15(12), P. 4982 - 5016

Published: Jan. 1, 2022

Here we consolidate recent advances in the fields of triplet–triplet annihilation photon upconversion and singlet fission. We further describe their utility increasing efficiency photovoltaic devices.

Language: Английский

Citations

73
Visible‐to‐UV Photon Upconversion: Recent Progress in New Materials and Applications DOI

Masanori Uji,

Till J. B. Zähringer, Christoph Kerzig

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(25)

Published: March 8, 2023

Ultraviolet (UV, λ<400 nm) light is essential for various photochemical reactions, but its intensity in the solar spectrum very low, and sources that artificially generate high-energy UV are inefficient environmentally unfriendly. A solution to this problem photon upconversion (UC) from visible (vis, λ>400 light. Among several mechanisms, UC based on triplet-triplet annihilation (TTA-UC) particular has made remarkable progress recent years. The development of new chromophores enabled highly efficient conversion low-intensity into In review, we summarize visible-to-UV TTA-UC, their production films application processes such as catalysis, bond activation polymerization. Finally, challenges opportunities future material applications will be discussed.

Language: Английский

Citations

52
Triplet–triplet annihilation photon upconversion-mediated photochemical reactions DOI
Ling Huang, Gang Han

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(4), P. 238 - 255

Published: March 21, 2024

Language: Английский

Citations

28
Excited Organic Radicals in Photoredox Catalysis DOI Creative Commons
Björn Pfund, Oliver S. Wenger

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 426 - 447

Published: Jan. 29, 2025

Many important synthetic-oriented works have proposed excited organic radicals as photoactive species, yet mechanistic studies raised doubts about whether they can truly function photocatalysts. This skepticism originates from the formation of (photo)redox-active degradation products and picosecond decay electronically radicals, which is considered too short for diffusion-based photoinduced electron transfer reactions. From this perspective, we analyze synthetic transformations where been photocatalysts, comparing their theoretical maximum state potentials with required observed photocatalytic reactivity. We summarize structurally similar photocatalysts indicating different reaction pathways some catalytic systems, addressing cases radical exceed Additionally, perform a kinetic analysis to explain in on subpicosecond time scales. further rationalize potential anti-Kasha reactivity higher states femtosecond lifetimes, highlighting how future photocatalysis advancements could unlock new photochemical pathways.

Language: Английский

Citations

4