B12‐Catalyzed Carbonylation of Carbon Tetrahalides: Using a Broad Range of Visible Light to Access Diverse Carbonyl Compounds DOI Creative Commons
Hisashi Shimakoshi, Keita Shichijo, Miho J. Tanaka

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

Abstract Visible‐light‐driven organic synthesis is a green and sustainable method for producing fine chemicals highly desirable at both laboratory industrial scales. In this study, we developed broad‐range (including the red region) visible‐light‐driven carbonylation of CCl 4 , CBr 3 F with nucleophiles, such as amines alcohols, using B 12 −Mg 2+ /TiO 2 hybrid catalyst. Carbonyl molecules ureas, carbamates, carbonate esters, carbamoyl fluorides were synthesized high selectivity efficiency under mild conditions. Diffuse reflectance UV‐vis spectroscopy, femtosecond time‐resolved diffuse density functional theory calculations revealed reaction mechanism combination S N single‐electron transfer. This rare example low‐energy, red‐light‐driven photocatalysis, which has been desired in recent years. We believe that study provides general platform to access diverse carbonyl could promote photocatalytic reactions on pilot scale.

Language: Английский

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

Near-infrared light-triggered prodrug photolysis by one-step energy transfer DOI Creative Commons
Kaiqi Long, Wen Lv, Zihan Wang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Dec. 7, 2023

Abstract Prodrug photolysis enables spatiotemporal control of drug release at the desired lesions. For photoactivated therapy, near-infrared (NIR) light is preferable due to its deep tissue penetration and low phototoxicity. However, most photocleavable groups cannot be directly activated by NIR light. Here, we report a upconversion-like process via only one step energy transfer for light-triggered prodrug photolysis. We utilize photosensitizer (PS) that can singlet-triplet (S-T) absorption achieve boron-dipyrromethene (BODIPY)-based prodrugs triplet-triplet transfer. Using strategy, green light-responsive with single-photon process. A wide range drugs bioactive molecules are designed demonstrated released under low-irradiance (100 mW/cm 2 , 5 min) high yields (up 87%). Moreover, micellar nanosystem encapsulating both PS developed demonstrate practicality our strategy in normoxia aqueous environment cancer therapy. This study may advance development photoresponsive delivery systems photo-activated

Language: Английский

Citations

23

Generation and Application of Aryl Radicals Under Photoinduced Conditions DOI
Anupam Das, K. R. Justin Thomas

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(31)

Published: March 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Language: Английский

Citations

13

Near–Infrared Heptamethine Cyanine Photosensitizers with Efficient Singlet Oxygen Generation for Anticancer Photodynamic Therapy DOI Open Access
Wenkai Liu, Shan He,

Xue Ma

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: July 31, 2024

Abstract Near‐infrared photosensitizers are valuable tools to improve treatment depth in photodynamic therapy (PDT). However, their low singlet oxygen ( 1 O 2 ) generation ability, indicated by quantum yield, presents a formidable challenge for PDT. To overcome this challenge, the heptamethine cyanine was decorated with biocompatible S Scy7 and Se Secy7 atom. We observe that exhibits redshift main absorption ~840 nm an ultra‐efficient capacity. The emergence of strong intramolecular charge transfer effect between atom polymethine chain considerably narrows energy gap (0.51 eV), heavy strengthens spin–orbit coupling (1.44 cm −1 ), both which greatly improved high triplet state yield (61 %), determines . Therefore, demonstrated excellent capacity, is ~24.5‐fold indocyanine green, ~8.2‐fold IR780, ~1.3‐fold methylene blue under low‐power‐density 850 irradiation (5 mW −2 ). considerable phototoxicity toward cancer cells buried 12 mm tissue. Nanoparticles formed encapsulating within amphiphilic polymers lecithin, promising antitumor anti‐pulmonary metastatic effects, exhibiting remarkable potential advancing PDT deep tissues.

Language: Английский

Citations

10

Low-energy photoredox catalysis DOI
David C. Cabanero, Tomislav Rovis

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

Language: Английский

Citations

10

Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions DOI Creative Commons
Han Li, Cui Wang, Felix Glaser

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 11402 - 11414

Published: May 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

Language: Английский

Citations

20

Recent advancements in the molecular design of deep-red to near-infrared light-absorbing photocatalysts DOI
Minling Zhong, Yujie Sun

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(8), P. 100973 - 100973

Published: April 17, 2024

Language: Английский

Citations

7

Hidden triplet states at hybrid organic–inorganic interfaces DOI
Guochen Bao, Renren Deng, Dayong Jin

et al.

Nature Reviews Materials, Journal Year: 2024, Volume and Issue: unknown

Published: July 26, 2024

Language: Английский

Citations

7

Red-Light-Promoted Radical Cascade Reaction to Access Tetralins and Dialins Enabled by Zinc(II)porphyrin, A Light-Flexible Catalyst DOI

Yusuke Okanishi,

Otoki Takemoto,

Sanpou Kawahara

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3929 - 3934

Published: April 26, 2024

[5,15-Bis(pentafluorophenyl)-10,20-diphenylporphinato]zinc(II) (1), a metalloporphyrin derivative that was recently reported as an efficient photocatalyst driven by blue LEDs our group, found to catalyze red-light-promoted (630 nm LEDs) radical cascade reaction of N-3-arylpropionyloxyphthalimides with radicophiles including electron-deficient alkenes and alkynes, providing access range functionalized tetralin dialin derivatives. The catalyzed 1 took place via oxidative quenching cycle in DMSO, where no sacrificial electron donor required, uncovering unique solvent effect capable promoting the porphyrin catalysis.

Language: Английский

Citations

6

Lead-free metal halide perovskites as the rising star in photocatalysis: The past, present, and prospective DOI
Girum Getachew, Aswandi Wibrianto, Akash S. Rasal

et al.

Progress in Materials Science, Journal Year: 2023, Volume and Issue: 140, P. 101192 - 101192

Published: Sept. 28, 2023

Language: Английский

Citations

16