Time-Resolved Spectroscopic Observation and Characterization of Water-Assisted Photoredox Reactions of Selected Aromatic Carbonyl Compounds

Abstract

Conspectus In recent years, unusual and efficient self-photoredox reactions were detected for selected benzophenone derivatives (BPs) and anthraquinone derivatives (AQs) in aqueous environments by Wan and co-workers, where the carbonyl undergoes reduction to the corresponding alcohol and a side-chain alcohol group undergoes oxidation to the corresponding carbonyl. To unravel the photoredox reaction mechanisms of these types of BPs and AQs in aqueous environments, we have utilized a combination of time-resolved spectroscopy techniques such as femtosecond transient absorption, nanosecond transient absorption, and nanosecond time-resolved resonance Raman spectroscopy to detect and characterize the electronic absorption and vibrational spectra of the intermediates and transient species from the femtosecond to microsecond time region after they are generated in the photoredox reactions. With the assistance of density functional theory calculations to simulate the electronic absorption and Raman spectra, the structural and kinetic information on the key reactive intermediates is described. Furthermore, the reaction pathways were calculated by finding the transition states connecting with the reactant and product complexes to better understand the photoredox reaction mechanism. In this Account, we summarize some of our time-resolved spectroscopic observations and characterization of water-assisted photoredox reactions of selected BPs and AQs. In the strong hydrogen-donor solvent isopropanol, the commonly studied photoreduction reaction for aromatic carbonyls via an intermolecular hydrogen atom tranfer process was observed for BPs and AQs. The photoredox reactions for the investigated BPs and AQs in aqueous environments occur on the triplet excited-state surface. Under moderately acidic aqueous conditions, the photoredox reactions for BPs and AQs are triggered by a proton transfer (PT) pathway. In neutral aqueous solutions, AQs may also undergo proton-coupled electron transfer (PCET) leading to the photoredox reaction, while BPs generate the ketyl radical species. Both BPs and AQs prefer the photohydration reaction in high-proton-concentration aqueous solutions (pH 0). The PT and PCET processes were found to offer more possibilities for the aromatic carbonyl compounds to lead to new photochemical reactions like the unusual photoredox reactions associated with BPs and AQs described here. Clear characterization of the photophysical pathways and the photochemical reactions of representative aromatic carbonyl compounds in aqueous environments not only provides fundamental information to better understand the photochemistry of carbonyl-containing compounds but also will facilitate the development of applications of these systems, like photochemical synthesis, drugs, and photolabile protecting groups. In addition, the importance of water molecules in the photochemical reactions of interest here may also lead to further understanding of how water influences the photochemistry of related carbonyl-containing compounds in aqueous ...

Mechanistic Investigations of an α-Aminoarylation Photoredox Reaction

“…21 Several other groups have utilized transient absorption spectroscopy to observe reaction intermediates in photoredox reactions. [22][23][24][25][26][27][28][29][30] α-arylamines and substituted nitrogen heterocycles are important structural motifs in medicinal and pharmaceutical chemistry. 31,35 Generation of these motifs using latent sp 3 C-H bonds via cross-coupling of amines and aryl building blocks has attracted significant attention, 32,33 with photoredox reactions representing a particularly attractive approach.…”

Disentangling Multiple Effects on Excited‐State Intramolecular Charge Transfer among Asymmetrical Tripartite PPI‐TPA/PCz Triads

“…Ultrafasttime-resolved transient absorption spectroscopy has become ap owerful technique to explore ar ange of excited states and CT dynamics of molecules. [39][40][41] By combination of femtosecond/nanosecond transient absorption (fs-TA/ns-TA) spectroscopy and excited-state theoretical calculations, the complete photophysical and photochemical behavior of PPI-TPA/PCz triads was elucidated.…”

“…Herein, compounds in which a PPI unit is coupled with two TPA or PCz moieties to form two kinds of asymmetrical ternary structures were designed and synthesized to explore the nature of the charge transfer (CT) in a series of asymmetrical tripartite PPI–TPA/PCz triads (Scheme 1). Ultrafast time‐resolved transient absorption spectroscopy has become a powerful technique to explore a range of excited states and CT dynamics of molecules [39–41] . By combination of femtosecond/nanosecond transient absorption (fs‐TA/ns‐TA) spectroscopy and excited‐state theoretical calculations, the complete photophysical and photochemical behavior of PPI‐TPA/PCz triads was elucidated.…”

Mechanistic Investigations of an α-Aminoarylation Photoredox Reaction

“…18,19 Several other groups have utilized transient absorption spectroscopy to observe reaction intermediates in photoredox reactions. [20][21][22][23][24][25][26][27][28] α-arylamines and substituted nitrogen heterocycles are important structural motifs in medicinal chemistry. 29 Generation of these motifs using latent sp 3 C-H bonds via cross-coupling of amines and aryl building blocks has attracted significant attention, 30,31 with photoredox reactions representing a particularly attractive approach.…”