Azido‐Bridged One‐Dimensional Mn (III) Polymers From Bidentate N, O‐Donor Schiff Bases: Crystal Structures and DFT Insights Into Spin Canting

ABSTRACT Five new one‐dimensional Mn (III) coordination polymers have been synthesized using bidentate N, O‐donor Schiff base ligands, representing the first examples of azido‐bridged Mn (III) chains derived from such ligands. Single‐crystal x‐ray diffraction reveals that all complexes adopt μ1,3‐azido bridging with distorted octahedral Mn (III) centers exhibiting characteristic Jahn–Teller elongation along the Mn‐N_azide axis. The Mn–Mn separations (5.43–5.82 Å) and azide‐mediated super‐exchange pathways indicate dominant antiferromagnetic interactions. First‐principles DFT (GGA+U) calculations show residual spin polarization due to intrachain spin canting arising from axial anisotropy. These findings highlight the structural‐electronic correlation governing spin alignment in azido‐bridged Mn (III) chains. Magnetic behavior discussed in this work is derived solely from DFT simulation, no bulk magnetic measurements are reported.