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1. Photochemistry of carbon nitrides and heptazine derivatives

   https://doi.org/10.1039/D1CC02745J  

   Hwang, Doyk; Schlenker, Cody W. (September 2021, Chemical Communications)

   We explore the photochemistry of polymeric carbon nitride (C 3 N 4 ), an archetypal organic photocatalyst, and derivatives of its structural monomer unit, heptazine (Hz). Through spectroscopic studies and computational analysis, we have observed that Hz derivatives can engage in non-innocent hydrogen bonding interactions with hydroxylic species. The photochemistry of these complexes is influenced by intermolecular nπ*/ππ* mixing of non-bonding orbitals of each component and the relative energy of intermolecular charge-transfer (CT) states. Coupling of the former to the latter appears to facilitate proton-coupled electron transfer (PCET), resulting in biradical products. We have also observed that Hz derivatives exhibit an extremely rare inverted singlet/triplet energy splitting (Δ E ST ). In violation of Hund's multiplicity rules, the lowest energy singlet (S 1 ) is stabilized relative to the lowest triplet (T 1 ) electronic excited state. Exploiting this unique inverted Δ E ST character has obvious implications for transformational discoveries in solid-state OLED lighting and photovoltaics. Harnessing this inverted Δ E ST , paired with light-driven intermolecular PCET reactions, may enable molecular transformations relevant for applications ranging from solar energy storage to new classes of non-triplet photoredox catalysts for pharmaceutical development. To this end, we have explored the possibility of optically controlling the photochemistry of Hz derivatives using ultrafast pump–push–probe spectroscopy. In this case, the excited state branching ratios among locally excited states of the chromophore and the reactive intermolecular CT state can be manipulated with an appropriate secondary “push” excitation pulse. These results indicate that we can predictively redirect chemical reactivity with light in this system, which is an avidly sought achievement in the field of photochemistry. Looking forward, we anticipate future opportunities for controlling heptazine photochemistry, including manipulating PCET reactivity with a diverse array of substrates and optically delivering reducing equivalents with, for example, water as a partial source of electrons and protons. Furthermore, we wholly expect that, over the next decade, materials such as Hz derivatives, that exhibit inverted Δ E ST character, will spawn a significant new research effort in the field of thin-film optoelectronics, where controlling recombination via triplet excitonic states can play a critical role in determining device performance. 

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2. Anomalous chemically induced electron spin polarization in proton-coupled electron transfer reactions: insight into radical pair dynamics

   https://doi.org/10.1039/d0sc02691c  

   Brugh, Alexander M.; Forbes, Malcolm D. (June 2020, Chemical Science)

   Time-resolved electron paramagnetic resonance (TREPR) spectroscopy has been used to study the proton coupled electron transfer (PCET) reaction between a ruthenium complex (Ru(bpz)(bpy) 2 ) and several substituted hydroquinones (HQ). After excitation at 355 nm, the HQ moiety forms a strong hydrogen bond to the exposed N atoms in the bpz heterocycle. At some point afterwards, a PCET reaction takes place in which an electron from the O atom of the hydrogen bond transfers to the metal center, and the proton forming the hydrogen bond remains on the bpz ligand N atom. The result is a semiquinone radical (HQ˙), whose TREPR spectrum is strongly polarized by the triplet mechanism (TM) of chemically induced dynamic electron spin polarization (CIDEP). Closer examination of the CIDEP pattern reveals, in some cases, a small amount of radical pair mechanism (RPM) polarization. We hypothesize that when the HQ moiety has electron donating groups (EDGs) substituted on the ring, S–T − RPM polarization is observed in HQ˙. These anomalous intensities are accounted for by spectral simulation using polarization from S–T − mixing. The generation of S–T − RPM is attributed to slow radical separation after PCET due to stabilization of the positive charge on the ring by EDGs. Results from a temperature dependence support the hypothesis. 

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3. Tyrosine, cysteine, and proton coupled electron transfer in a ribonucleotide reductase-inspired beta hairpin maquette

   https://doi.org/10.1039/C9CC04067F  

   McCaslin, Tyler G.; Pagba, Cynthia V.; Hwang, Hyea; Gumbart, James C.; Chi, San-Hui; Perry, Joseph W.; Barry, Bridgette A. (August 2019, Chemical Communications)

   Tyrosine residues act as intermediates in proton coupled electron transfer reactions (PCET) in proteins. For example, in ribonucleotide reductase (RNR), a tyrosyl radical oxidizes an active site cysteine via a 35 Å pathway that contains multiple aromatic groups. When singlet tyrosine is oxidized, the radical becomes a strong acid, and proton transfer reactions, which are coupled with the redox reaction, may be used to control reaction rate. Here, we characterize a tyrosine-containing beta hairpin, Peptide O, which has a cross-strand, noncovalent interaction between its single tyrosine, Y5, and a cysteine (C14). Circular dichroism provides evidence for a thermostable beta-turn. EPR spectroscopy shows that Peptide O forms a neutral tyrosyl radical after UV photolysis at 160 K. Molecular dynamics simulations support a phenolic/SH interaction in the tyrosine singlet and radical states. Differential pulse voltammetry exhibits pH dependence consistent with the formation of a neutral tyrosyl radical and a p K a change in two other residues. A redox-coupled decrease in cysteine p K a from 9 (singlet) to 6.9 (radical) is assigned. At pD 11, picosecond transient absorption spectroscopy after UV photolysis monitors tyrosyl radical recombination via electron transfer (ET). The ET rate in Peptide O is indistinguishable from the ET rates observed in peptides containing a histidine and a cyclohexylalanine (Cha) at position 14. However, at pD 9, the tyrosyl radical decays via PCET, and the decay rate is slowed, when compared to the histidine 14 variant. Notably, the decay rate is accelerated, when compared to the Cha 14 variant. We conclude that redox coupling between tyrosine and cysteine can act as a PCET control mechanism in proteins. 

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4. Panoramic portrait of primary molecular events preceding excited state proton transfer in water

   https://doi.org/10.1039/C6SC00672H  

   Liu, Weimin; Wang, Yanli; Tang, Longteng; Oscar, Breland G.; Zhu, Liangdong; Fang, Chong (January 2016, Chemical Science)

   Photochemistry powers numerous processes from luminescence and human vision, to light harvesting. However, the elucidation of multidimensional photochemical reaction coordinates on molecular timescales remains challenging. We developed wavelength-tunable femtosecond stimulated Raman spectroscopy to simultaneously achieve pre-resonance enhancement for transient reactant and product species of the widely used photoacid pyranine undergoing excited-state proton transfer (ESPT) reaction in solution. In the low-frequency region, the 280 cm −1 ring deformation mode following 400 nm photoexcitation exhibits pronounced intensity oscillations on the sub-picosecond timescale due to anharmonic vibrational coupling to the 180 cm −1 hydrogen-bond stretching mode only in ESPT-capable solvents, indicating a primary event of functional relevance. This leads to the contact ion pair formation on the 3 ps timescale before diffusion-controlled separation. The intermolecular 180 cm −1 mode also reveals vibrational cooling time constants, ∼500 fs and 45 ps in both H 2 O and D 2 O, which differ from ESPT time constants of ∼3/8 and 90/250 ps in H 2 O/D 2 O, respectively. Spectral results using H 2 18 O further substantiate the functional role of the intermolecular 180 cm −1 mode in modulating the distance between proton donor and acceptor and forming the transient ion pair. The direct observation of molecular structural evolution across a wide spectral region during photochemical reactions enriches our fundamental understanding of potential energy surface and holds the key to advancing energy and biological sciences with exceptional atomic and temporal precision. 

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5. Ultrafast Spectroscopies of Nitrophenols and Nitrophenolates in Solution: From Electronic Dynamics and Vibrational Structures to Photochemical and Environmental Implications

   https://doi.org/10.3390/molecules28020601  

   Bailey-Darland, Sullivan; Krueger, Taylor D.; Fang, Chong (January 2023, Molecules)

   Nitrophenols are a group of small organic molecules with significant environmental implications from the atmosphere to waterways. In this work, we investigate a series of nitrophenols and nitrophenolates, with the contrasting ortho-, meta-, and para-substituted nitro group to the phenolic hydroxy or phenolate oxygen site (2/3/4NP or NP−), implementing a suite of steady-state and time-resolved spectroscopic techniques that include UV/Visible spectroscopy, femtosecond transient absorption (fs-TA) spectroscopy with probe-dependent and global analysis, and femtosecond stimulated Raman spectroscopy (FSRS), aided by quantum calculations. The excitation-dependent (400 and 267 nm) electronic dynamics in water and methanol, for six protonated or deprotonated nitrophenol molecules (three regioisomers in each set), enable a systematic investigation of the excited-state dynamics of these functional “nanomachines” that can undergo nitro-group twisting (as a rotor), excited-state intramolecular or intermolecular proton transfer (donor–acceptor, ESIPT, or ESPT), solvation, and cooling (chromophore) events on molecular timescales. In particular, the meta-substituted compound 3NP or 3NP− exhibits the strongest charge-transfer character with FSRS signatures (e.g., C–N peak frequency), and thus, does not favor nitroaromatic twist in the excited state, while the ortho-substituted compound 2NP can undergo ESIPT in water and likely generate nitrous acid (HONO) after 267 nm excitation. The delineated mechanistic insights into the nitro-substituent-location-, protonation-, solvent-, and excitation-wavelength-dependent effects on nitrophenols, in conjunction with the ultraviolet-light-induced degradation of 2NP in water, substantiates an appealing discovery loop to characterize and engineer functional molecules for environmental applications. 

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