A number of pentacoordinated gallium complexes iSQ(2)GaR (1-7) (R = Et (1), Me (2), N-3 (3), Cl (4), Br (5), I(6), NCS (7)) where iSQ is a radical anion of 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone were synthesized, and crystalline samples of 1-7 were characterized using magnetic susceptibility measurements. The character of magnetic exchange interaction between spins of o-iminosemiquinonate radicals was found to be strongly influenced by the nature of the apical substituent. The antiferromagnetic coupling is predominant when the apical position is occupied by halogens or other tested inorganic anions, and the value of exchange interaction parameter varies from -99 to -176 K for R = I and NCS, respectively. In the case of groups the ferromagnetic exchange prevails and, as the result, the triplet ground state for pentacoordianted biradical compounds was observed. Compounds 1-7 demonstrate a biradical X-band EPR spectrum in frozen toluene matrix. The molecular structures of 4, 6, and 7 have been established by single-crystal X-ray analysis. A computational DFT UB3LYP/6-31G(d,p) study was performed on complexes 1-7 in order to understand the reason for changes in the magnetic behavior of the related diradical gallium compounds. The calculations showed that the magnetic behavior of the complexes with inorganic anions is conditioned by the presence of antiferromagnetic exchange channel formed as a consequence of overlapping between donor atomic orbitals of iminoquinone with pi-orbitals of halogen atoms (4-6) or nitrogen atom (3, 7).