Two new vanadyl complexes of N-confused porphyrins (NCPs), [VONCTPP] () and [VONCP(OMe)] (), have been synthesized for the first time and investigated as a catalyst for the oxidative bromination reaction of phenol and its derivatives. This article further delineates crystal structures, photophysical, and redox properties of both the vanadyl complexes. Complexes and exhibited a significant red shift in their absorption spectra compared with their respective free bases. The single-crystal structure of revealed that the complex is in the 2H tautomeric form, while EPR studies revealed the +4 oxidation state of vanadium metal having an axial compression with d configuration. Catalytic potential for -like activity has been explored for both complexes and for the first time in NCP chemistry with excellent TOF values (4.7-6.3 s for and 7.3-8.7 s for ) using KBr as a source of bromine and HO as a green oxidant in aqueous acidic medium at 298 K. Notably, both catalysts show excellent recyclability over five cycles. The vanadyl-metalated NCPs exhibit excellent stability in the air.
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