TY - JOUR
T1 - Local Hydrogen Bonding Determines Branching Pathways in Intermolecular Heptazine Photochemistry
AU - Hwang, Doyk
AU - Wrigley, Liam M.
AU - Lee, Micah
AU - Sobolewski, Andrzej L.
AU - Domcke, Wolfgang
AU - Schlenker, Cody W.
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/8/3
Y1 - 2023/8/3
N2 - Heptazine is the molecular core of the widely studied photocatalyst carbon nitride. By analyzing the excited-state intermolecular proton-coupled electron-transfer (PCET) reaction between a heptazine derivative and a hydrogen-atom donor substrate, we are able to spectroscopically identify the resultant heptazinyl reactive radical species on a picosecond time scale. We provide detailed spectroscopic characterization of the tri-anisole heptazine:4-methoxyphenol hydrogen-bonded intermolecular complex (TAHz:MeOPhOH), using femtosecond transient absorption spectroscopy and global analysis, to reveal distinct product absorption signatures at ∼520, 1250, and 1600 nm. We assign these product peaks to the hydrogenated TAHz radical (TAHzH•) based on control experiments utilizing 1,4-dimethoxybenzene (DMB), which initiates electron transfer without concomitant proton transfer, i.e., no excited-state PCET. Additional control experiments with radical quenchers, protonation agents, and UV-vis-NIR spectroelectrochemistry also corroborate our product peak assignments. These spectral assignments allowed us to monitor the influence of the local hydrogen-bonding environment on the resulting evolution of photochemical products from excited-state PCET of heptazines. We observe that the preassociation of heptazine with the substrate in solution is extremely sensitive to the hydrogen-bond-accepting character of the solvent. This sensitivity directly influences which product signatures we detect with time-resolved spectroscopy. The spectral signature of the TAHzH• radical assigned in this work will facilitate future in-depth analysis of heptazine and carbon nitride photochemistry. Our results may also be utilized for designing improved PCET-based photochemical systems that will require precise control over local molecular environments. Examples include applications such as preparative synthesis involving organic photoredox catalysis, on-site solar water purification, as well as photocatalytic water splitting and artificial photosynthesis.
AB - Heptazine is the molecular core of the widely studied photocatalyst carbon nitride. By analyzing the excited-state intermolecular proton-coupled electron-transfer (PCET) reaction between a heptazine derivative and a hydrogen-atom donor substrate, we are able to spectroscopically identify the resultant heptazinyl reactive radical species on a picosecond time scale. We provide detailed spectroscopic characterization of the tri-anisole heptazine:4-methoxyphenol hydrogen-bonded intermolecular complex (TAHz:MeOPhOH), using femtosecond transient absorption spectroscopy and global analysis, to reveal distinct product absorption signatures at ∼520, 1250, and 1600 nm. We assign these product peaks to the hydrogenated TAHz radical (TAHzH•) based on control experiments utilizing 1,4-dimethoxybenzene (DMB), which initiates electron transfer without concomitant proton transfer, i.e., no excited-state PCET. Additional control experiments with radical quenchers, protonation agents, and UV-vis-NIR spectroelectrochemistry also corroborate our product peak assignments. These spectral assignments allowed us to monitor the influence of the local hydrogen-bonding environment on the resulting evolution of photochemical products from excited-state PCET of heptazines. We observe that the preassociation of heptazine with the substrate in solution is extremely sensitive to the hydrogen-bond-accepting character of the solvent. This sensitivity directly influences which product signatures we detect with time-resolved spectroscopy. The spectral signature of the TAHzH• radical assigned in this work will facilitate future in-depth analysis of heptazine and carbon nitride photochemistry. Our results may also be utilized for designing improved PCET-based photochemical systems that will require precise control over local molecular environments. Examples include applications such as preparative synthesis involving organic photoredox catalysis, on-site solar water purification, as well as photocatalytic water splitting and artificial photosynthesis.
UR - http://www.scopus.com/inward/record.url?scp=85166442352&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.3c01397
DO - 10.1021/acs.jpcb.3c01397
M3 - Article
C2 - 37471476
AN - SCOPUS:85166442352
SN - 1520-6106
VL - 127
SP - 6703
EP - 6713
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 30
ER -