Inducing Antiferromagnetism in a Vinylene-linked 2D Covalent Organic Framework via Metal Complex Anchoring

Abstract

In a proof-of-concept study, we report the synthesis of a vinylene-linked covalent organic framework (TMT-PPy COF) featuring pyridyl anchoring sites for post-synthetic metallation. Through site-specific C-H activation with an Ir(III) complex, the metal-anchored IrCp*Cl@TMT-PPy was synthesized. While both the pristine TMT-PPy and the precursor Ir-complex are diamagnetic, magnetic susceptibility measurements reveal the emergence of antiferromagnetic interactions in IrCp*Cl@TMT-PPy (µ_eff = 1.09 µB; θ_CW = -411 K). Theoretical analyses suggest that the observed magnetic behavior originates from framework-assisted electronic perturbations induced upon metallation, highlighting a new route toward magnetic COF materials.