Benzo[c][1,2,5]Thiadiazole Linkers Enhance the Effectiveness of Cavity‐Containing Supramolecular Photocatalysts
- 1Institute of Chemical Sciences, Heriot‐Watt University Riccarton, Edinburgh UK
Abstract
A family of seven novel supramolecular photosensitizers comprising benzo[c][1,2,5]thiadiazole (BTZ) tethered calix[4]arene (C[4]) scaffolds has been synthesized using cross‐coupling strategies with selectively halogenated C[4]s, affording target compounds in high yield using facile purification. Their respective abilities to produce singlet oxygen has been evaluated through the photo‐oxidation of α‐terpinene, and structure–activity relationships established, probing factors such as cavity:photosensitizer ratio, distance of cavity to photosensitizer linker, and steric hindrance around the upper‐rim of the cavity. The presence of two C[4] cavities proximal to the photosensitizing BTZ unit provided vastly increased effectiveness in enhancing effective concentration through host:guest interactions, resulting in an eightfold increase in efficiency for the best‐performing member of the compound library benchmarked against a small‐molecule analogue, and reaching reaction completion in 1 h at 2.5 mol% loading. In contrast, systematically increasing the cavity:photosensitizing linker distance led to a reduction in improvement to 1.1‐fold relative to the small molecule analogue, confirming that these factors are pivotal in designing a suitable system based on the guest substrate.
Related
- Antimony(III) and Bismuth(III) Halide Complexes Containing Thiazole-and Thiadiazole-Based Mercapto Ligands: Synthesis, Structural Characterization, and Biological Activity
- Triaryl-Heptazine Photocatalysts for the Oxidation of C–H and C–C Bonds in Nitrogen-Containing Molecules
- Design, synthesis, and biological evaluation of novel 4,5-diaryl-1,2,3-thiadiazole derivatives: anticancer activity and molecular docking studies
- In vitro and in silico evaluation of antifungal potential of 2-amino-5-(3-nitrophenyl)-1,3,4-thiadiazole against aspergillus niger: implications for nanotechnology-based antifungal design
- LinkerGen: Guided Autoregressive Generation of Organic Linkers for Reticular Chemistry
BibTeX
@article{amicosante2026benzoc125thiadiazole,
title = {{Benzo[c][1,2,5]Thiadiazole Linkers Enhance the Effectiveness of Cavity‐Containing Supramolecular Photocatalysts}},
author = {Leonardo Amicosante and Dominic Taylor and Cameron L. Campbell and Daniel M. Lambden and Georgina M. Rosair and Filipe Vilela and Scott J. Dalgarno},
journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = aug,
doi = {10.1002/chem.71443},
url = {https://doi.org/10.1002/chem.71443},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Benzo[c][1,2,5]Thiadiazole Linkers Enhance the Effectiveness of Cavity‐Containing Supramolecular Photocatalysts
AU - Leonardo Amicosante
AU - Dominic Taylor
AU - Cameron L. Campbell
AU - Daniel M. Lambden
AU - Georgina M. Rosair
AU - Filipe Vilela
AU - Scott J. Dalgarno
PY - 2026
DA - 2026/08/03
JO - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/chem.71443
UR - https://doi.org/10.1002/chem.71443
AB - A family of seven novel supramolecular photosensitizers comprising benzo[c][1,2,5]thiadiazole (BTZ) tethered calix[4]arene (C[4]) scaffolds has been synthesized using cross‐coupling strategies with selectively halogenated C[4]s, affording target compounds in high yield using facile purification. Their respective abilities to produce singlet oxygen has been evaluated through the photo‐oxidation of α‐terpinene, and structure–activity relationships established, probing factors such as cavity:photosensitizer ratio, distance of cavity to photosensitizer linker, and steric hindrance around the upper‐rim of the cavity. The presence of two C[4] cavities proximal to the photosensitizing BTZ unit provided vastly increased effectiveness in enhancing effective concentration through host:guest interactions, resulting in an eightfold increase in efficiency for the best‐performing member of the compound library benchmarked against a small‐molecule analogue, and reaching reaction completion in 1 h at 2.5 mol% loading. In contrast, systematically increasing the cavity:photosensitizing linker distance led to a reduction in improvement to 1.1‐fold relative to the small molecule analogue, confirming that these factors are pivotal in designing a suitable system based on the guest substrate.
SN - 0947-6539
SN - 1521-3765
ER -