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使用密度泛函理论和定性轨道分析方法研究了六配位锇(Ⅳ)叶啉络合物[Os(por)L_2](L=CH_3,OCH_3,SCH_3,SeCH_3,Cl,Br,I)中不同的轴向配体对络合物的结构和磁性的影响.结果表明,不同性质的轴向配体对锇的两个e_g轨道(即d_(xz)和d_(yz))的影响不同,导致锇具有不同的电子组态:(1)当轴向配体为反位影响很强的CH_3时,L—Os—L弯曲,这种弯曲导致d_(xz)和d_(yz)轨道能级分裂,整个络合物表现为弯曲抗磁;(2)当轴向配体为反位影响很弱的OCH_3,SCH_3,SeCH_3以及卤素Cl,Br,I时,L—Os—L均保持线性,其中单面π供体性较强的SCH_3,SeCH_3,使得d_(xz)和d_(yz),轨道能级有较大的分裂,络合物呈线性抗磁;单面π供体性较弱的OCH_3,其d_(xz)和d_(yz)轨道能级分裂较小,整个络合物呈线性顺磁;卤素则由于其双面π供体的等同性,使得它对d_(xz)和d_(yz)轨道的影响一样,其简并性仍得以保持,络合物也表现为线性顺磁.
The effects of six coordination osmium (Ⅳ) phyllorphic complexes [Os (por) L_2] (L = CH_3, OCH_3, SCH_3, SeCH_3, Cl, Br, I) were studied using density functional theory and qualitative orbit analysis Of the axial ligands on the structure and magnetism of the complexes.The results show that the different axial ligands have different effects on the two e_g orbitals (ie d_ (xz) and d_ (yz)) of osmium, resulting in Osmium has a different electronic configuration: (1) L-Os-L bends when the axial ligand is CH_3, which strongly affects the anti-position. This bending leads to splitting of the energy levels of d_ (xz) and d_ (yz) (2) When the axial ligands are OCH_3, SCH_3, SeCH_3 and halogen Cl, Br, I, L-Os-L remain linear in the axial ligands, The single-sided π-donor SCH_3 and SeCH_3 make the d_ (xz) and d_ (yz), the orbital energy levels have a larger splitting, and the complexes are linearly diamagnetic. The single-sided π-donor is weak OCH_3 has a small energy level splitting at d_ (xz) and d_ (yz) orbital, and the entire complex is linearly paramagnetic. Due to its isomorphism of π-donors on both sides, (yz) orbit, its degeneracy is still maintained, the complex also showed linear paramagnetic.