N-aminated N-heterocycle based hydrazones as widely tunable photoswitches
7 affiliations
- 1School of Chemistry and Chemical Engineering
- 2University of Southampton Southampton
- 3Department of Chemistry – Ångström Laboratory
- 4Uppsala University
- 5EaStCHEM, School of Chemistry
- 6University of St Andrews
- 7Institute for Life Sciences
Abstract
Photoswitches based on E/Z isomerism around a C=N bond have found wide-reaching applications in materials science and biology. Herein, we report a new class of hydrazone photoswitch based on aminated nitrogen heterocycles, the N-aminated N-heterocyclic hydrazones (NaNs). These photoswitches can be synthesised in a single step, achieve near quantitative photoswitching, offer visible light (470 nm) response, have thermal half-lives of up to 958 hours at room temperature and quantum yields of up to 70%. We have investigated the impact of different structural features on switch properties by studying a library of 30 derivatives with varied N-amino N-heterocyclic components and varied aldehyde components. These have been extensively studied in the solution and solid state, towards understanding structure-activity relationships for rational NaN photoswitch design. The stability of the metastable state facilitated the growth of the Z-isomer crystals for an anthracene derived NaN, and we observed both E/Z isomerisation and dimerisation of the anthracene, depending on irradiation duration. Furthermore, we demonstrate a member of the library undergoes E→Z photoisomerisation in the solid state, displaying single crystal to single crystal switching. We anticipate that the simple synthesis of these compounds, combined with their tuneable properties, will ensure that they find widespread application across numerous fields.
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BibTeX
@misc{buchanan2026naminated,
title = {{N-aminated N-heterocycle based hydrazones as widely tunable photoswitches}},
author = {Alex Buchanan and Rebecca Kerridge and Jorn Steen and Alexander M. Wilmshurst and Daniel Rainer and Finlay Williams and Alexandra Reynolds and Neil Wells and Jiarong Wu and Jake L. Greenfield and Graham Tizzard and Stefano Crespi and George T. Williams},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009959/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009959/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - N-aminated N-heterocycle based hydrazones as widely tunable photoswitches
AU - Alex Buchanan
AU - Rebecca Kerridge
AU - Jorn Steen
AU - Alexander M. Wilmshurst
AU - Daniel Rainer
AU - Finlay Williams
AU - Alexandra Reynolds
AU - Neil Wells
AU - Jiarong Wu
AU - Jake L. Greenfield
AU - Graham Tizzard
AU - Stefano Crespi
AU - George T. Williams
PY - 2026
DA - 2026/10/05
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009959/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009959/v1
AB - Photoswitches based on E/Z isomerism around a C=N bond have found wide-reaching applications in materials science and biology. Herein, we report a new class of hydrazone photoswitch based on aminated nitrogen heterocycles, the N-aminated N-heterocyclic hydrazones (NaNs). These photoswitches can be synthesised in a single step, achieve near quantitative photoswitching, offer visible light (470 nm) response, have thermal half-lives of up to 958 hours at room temperature and quantum yields of up to 70%. We have investigated the impact of different structural features on switch properties by studying a library of 30 derivatives with varied N-amino N-heterocyclic components and varied aldehyde components. These have been extensively studied in the solution and solid state, towards understanding structure-activity relationships for rational NaN photoswitch design. The stability of the metastable state facilitated the growth of the Z-isomer crystals for an anthracene derived NaN, and we observed both E/Z isomerisation and dimerisation of the anthracene, depending on irradiation duration. Furthermore, we demonstrate a member of the library undergoes E→Z photoisomerisation in the solid state, displaying single crystal to single crystal switching. We anticipate that the simple synthesis of these compounds, combined with their tuneable properties, will ensure that they find widespread application across numerous fields.
ER -