Nitronyl nitroxide radical 1, NIT (4, 4, 5, 5-tetramethyl-4, 5-dihydro-1H-imidazolyl-1- oxyl-3-oxide) and copper(II) chloride complexes with nitronyl nitroxide 2, [Cu(NITPh)2Cl2] (NITPh = 2-phenyl-4, 4, 5, 5-tetrameth...Nitronyl nitroxide radical 1, NIT (4, 4, 5, 5-tetramethyl-4, 5-dihydro-1H-imidazolyl-1- oxyl-3-oxide) and copper(II) chloride complexes with nitronyl nitroxide 2, [Cu(NITPh)2Cl2] (NITPh = 2-phenyl-4, 4, 5, 5-tetramethyl-imidazoline-1-oxyl-3-oxide) were studied with density functional theory (DFT). The magnetic orbital analysis reveals that the antiferromagnetic coupling for complex 2 is due to the antibonding s*-orbital overlap between 22x-yd(Cu) and p* (NO) orbitals. Also, spin population and atomic charge distribution analysis suggest that for AFS of complex 2 the antiferromagnetic coupling between the radical ligands and the copper(II) ion originates from the spin delocalization induced by the a electron transfer from p*(NO) to 22x-yd(Cu) orbital.展开更多
文摘Nitronyl nitroxide radical 1, NIT (4, 4, 5, 5-tetramethyl-4, 5-dihydro-1H-imidazolyl-1- oxyl-3-oxide) and copper(II) chloride complexes with nitronyl nitroxide 2, [Cu(NITPh)2Cl2] (NITPh = 2-phenyl-4, 4, 5, 5-tetramethyl-imidazoline-1-oxyl-3-oxide) were studied with density functional theory (DFT). The magnetic orbital analysis reveals that the antiferromagnetic coupling for complex 2 is due to the antibonding s*-orbital overlap between 22x-yd(Cu) and p* (NO) orbitals. Also, spin population and atomic charge distribution analysis suggest that for AFS of complex 2 the antiferromagnetic coupling between the radical ligands and the copper(II) ion originates from the spin delocalization induced by the a electron transfer from p*(NO) to 22x-yd(Cu) orbital.
