Magnetic Modulation in Heteroallene and Heterocumulene Based tert‐butyl Nitroxide Diradicals: Spin Delocalization and Conformation Play Crucial Roles

Abstract We have theoretically investigated the magnetic properties of heteroallene (>C=C=X−) and heterocumulene (>C=C=C=X−) based tert ‐butyl nitroxide diradicals (X is P/As). Calculation of magnetic exchange coupling constant ( J ) shows ferromagnetic interaction in heteroallene based diradicals. Whereas, in heterocumulene based diradicals, tuning of J value from antiferro‐ to ferro‐magnetic state is observed from Z ‐ to E ‐ isomer. Delocalization of spin density from radical site to the coupler (in planar arrangement) is observed in spin distribution analysis which is also advocated by molecular orbital analysis. The typical feature of tert ‐butyl nitroxide radical creates spin delocalization along with spin polarization within the coupler. The J values of all the diradicals strongly depend on the dihedral angle between radical center and coupler. Magneto‐structural correlation shows that the change in dihedral angle tunes the magnetic property for both the Z ‐ and E ‐ isomers of heterocumulenes depending on the spin accumulation on two nearby magnetic centers. The extent of spin delocalization and conformation of spin centers on the molecular axis are important for the different J values observed in our designed systems.