High spin ground state copper(II) and nickel(II) complexes possessing the 3,5-di-tert-butyl-1,2-semiquinonate radical anion
作者： Royce A. Davidson , Jingjun Hao , Arnold L. Rheingold , Joel S. Miller
DOI: 10.1016/J.POLY.2017.05.038
关键词: Chemistry 、 Excited state 、 Square pyramidal molecular geometry 、 Unpaired electron 、 Nickel 、 Computational chemistry 、 Crystallography 、 Ground state 、 Singlet state 、 Octahedron 、 Copper
摘要: Abstract Several high spin ground-state compounds based upon ferromagnetic coupling between a metal ion and the chelating 3,5-di-tert-butyl-1,2-semiquinonate radical anion, [DTBSQ] −, as they possess unpaired electron spins in orthogonal dx2−y2/dz2 π∗ orbitals, are described. [CuII(DPyA)(DTBSQ)](ClO4) (DPyA = 2,2′-dipyridylamine) was reinvestigated its singlet excited state is 282 cm−1 [0.035 eV; J/kB = 406 K (H = −JSa·Sb)] above triplet ground state. [CuII(bipy)(DBCat)(MeOH)] (bipy = 2,2-bipyridine; DBCat = 3,5-di-tert-butylcatecholate), [CuII(bipy)(DTBSQ)](BF4), [CuII(DPyA)(DTBSQ)-(THF)2](BF4) [NiII(DPyA)(DTBSQ)(THF)2](BF4) have been structurally characterized states whose low lie 28 cm−1 (0.0034 eV), 382 cm−1 (0.047 eV), 335 cm−1 (0.042 eV), 108 cm−1 (0.013 eV) higher, respectively. The triplet-singlet separation 18% greater for [CuII(DPyA)(DTBSQ)(THF)2]+ than [CuII(DPyA)(DTBSQ)]+ ascribed to orthogonality of CuII − orbitals octahedral [Cu(DPyA)(DTBSQ)(THF)2]+ with respect distorted square pyramidal structure [Cu(DPyA)(DTBSQ)]+. This energy correlates shorter average M-ODTBSQ distance, i.e. [Cu(bipy)(DTBSQ)]+ > [CuII(DPyA)(DTBSQ)(THF)2]+ > [Ni(DPyA)(DTBSQ)(THF)2]+. order magnitude lower value arises from weak intradimer S = 1/2 Cu(II) interaction, not via sites.
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