A photocatalytic
chemodivergent reaction for the selectivity formation
of C–S and C–N bonds in a controlled manner was proposed.
The reaction medium, either neutral or acidic, is critical to dictate
the formation of 2-amino-1,3,4-thiadiazoles and 1,2,4-triazole-3-thiones
from isothiocyanates and hydrazones. This is a practical protocol
to achieve the chemoselectivity under mild and metal-free conditions.