Effect of cyano-addition on the photoacidity switch in 5-cyano-8-amino-2-naphthol

Literature Information

Publication Date 2023-11-29
DOI 10.1039/D3CP04845D
Impact Factor 3.676
Authors

Jialin Xie, Rachel E. Nealon, Zelia T. Egan, Kana Takematsu


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Abstract

Cyano- or CN-additions are often utilized in the design of photoacids to enhance and/or enable excited state proton transfer (ESPT) from the protic site to aqueous and nonaqueous solvents. In diprotic photoacid 8-amino-2-naphthol (8N2OH), the protonation state of the amino group (NH3+/NH2) acts as an on–off switch for ESPT at the OH site in water. This study investigated whether the addition of CN in 5-cyano-8-amino-2-naphthol (5CN8) could override this switch and promote new ESPT pathways. Analysis of the steady-state and time-resolved emission data showed that in the presence of protonated NH3+, CN enhances OH photoacidity (vs. in 8N2OH) and activates the ESPT pathway at NH3+. Both protic sites, OH and NH3+, can also donate a proton to methanol upon excitation. In contrast, in the presence of deprotonated NH2, despite the addition of CN, ESPT is still not observed at the OH site for 5CN8. Thus, the addition of CN cannot override or negate the inhibiting effect of NH2 on OH photoacidity. Potential causes for this inhibition are discussed, including electronic and antiaromaticity effects of CN and NH2 substitution.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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