Examining the nature of π and σ orbitals in the diradical dications can reveal the reason for the switching of magnetic exchange upon bending. In perfectly planar molecules, the π orbitals are formed purely by the overlap of p z orbitals and are distinct from σ orbitals. When bending is introduced, the distinction between π and σ orbitals gets blurred, and the frontier π orbitals start acquiring some σ character. This mixing of the σ and π orbitals results in spin polarization of the core σ orbitals, resulting in greater spin density delocalization resulting from the same. We observe that among the three diradical dications, TeH 2+•• has the least π bond character for SOMOs and the highest spin density delocalization via σ bonds (Table. S10). The mixing of σ and π bond characters can alter the energy levels of the frontier orbitals and influence the magnetic coupling in the ground state. In a planar diradical dication, the SOMOs will ideally be nearly degenerate. However, when bending is introduced, σ-π mixing occurs and the energy splitting of SOMOs increases. When the pairing energy of electrons is greater than the ∆E ss as in the case of SH 2+•• and SeH 2+•• , the molecule will have ferromagnetic coupling. However, when the value of ∆E ss is greater than the pairing energy, the electron from the more energetic SOMO will jump to the lower SOMO and form a singlet state as in the case of TeH 2+•• .