Photochemical Carbamate Scission Redefines Metal-Based PhotoCORMs through Multi-Output Activation
Abstract
Metal-based photoCORMs (Photoactivatable carbon monoxide-releasing molecules) have traditionally relied on photolabile M–CO bonds, constraining modular design and limiting opportunities for integrating additional functions. Here we report a modular metalbased platform in which CO generation is encoded within a photolabile carbamate rather than a M–CO bond, enabling visible-light-controlled, spatiotemporal CO release while preserving the synthetic flexibility to integrate multimodal functions within a single molecular architecture. As a proof of concept, we constructed a fluorogenic, CA-IX-targeted Pt(IV) complex in which a naphthalimide chromophore is coupled to the metal centre through a carbamate CO-releasing module. Photoexcitation of the chromophore initiates a programmed cascade comprising carbamate scission for CO release along with fluorogenic activation of the CA-IX-inhibiting dye, and reduction of Pt(IV) to cytotoxic Pt(II), validating the modular design. More broadly, this work demonstrates that carbamate photolysis provides a broadly applicable route to programmable, stimuli-controlled CO release, independent of metal–carbonyl chemistry, integrated with modular multifunctional therapeutic architectures.
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BibTeX
@misc{halder2026photochemical,
title = {{Photochemical Carbamate Scission Redefines Metal-Based PhotoCORMs through Multi-Output Activation}},
author = {Rakesh Halder and Shamik Chanda and Manisha Rathore and Sayar Ghosh and Joshua Stephen Kingsley and Simone Giovannuzzi and Subhendu Karmakar and Goutam Sahoo and Shilpendu Ghosh and Gendan Lal and Aniruddha Das and Claudiu T Supuran and Rajdeep Guha and Rahul Das and Sandeep Singh and Sangita Sen and Arindam Mukherjee},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008336/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008336/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Photochemical Carbamate Scission Redefines Metal-Based PhotoCORMs through Multi-Output Activation
AU - Rakesh Halder
AU - Shamik Chanda
AU - Manisha Rathore
AU - Sayar Ghosh
AU - Joshua Stephen Kingsley
AU - Simone Giovannuzzi
AU - Subhendu Karmakar
AU - Goutam Sahoo
AU - Shilpendu Ghosh
AU - Gendan Lal
AU - Aniruddha Das
AU - Claudiu T Supuran
AU - Rajdeep Guha
AU - Rahul Das
AU - Sandeep Singh
AU - Sangita Sen
AU - Arindam Mukherjee
PY - 2026
DA - 2026/09/04
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008336/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008336/v1
AB - Metal-based photoCORMs (Photoactivatable carbon monoxide-releasing molecules) have traditionally relied on photolabile M–CO bonds, constraining modular design and limiting opportunities for integrating additional functions. Here we report a modular metalbased platform in which CO generation is encoded within a photolabile carbamate rather than a M–CO bond, enabling visible-light-controlled, spatiotemporal CO release while preserving the synthetic flexibility to integrate multimodal functions within a single molecular architecture. As a proof of concept, we constructed a fluorogenic, CA-IX-targeted Pt(IV) complex in which a naphthalimide chromophore is coupled to the metal centre through a carbamate CO-releasing module. Photoexcitation of the chromophore initiates a programmed cascade comprising carbamate scission for CO release along with fluorogenic activation of the CA-IX-inhibiting dye, and reduction of Pt(IV) to cytotoxic Pt(II), validating the modular design. More broadly, this work demonstrates that carbamate photolysis provides a broadly applicable route to programmable, stimuli-controlled CO release, independent of metal–carbonyl chemistry, integrated with modular multifunctional therapeutic architectures.
ER -