XPS and quantum chemical investigation of electronic structure of Co complexes with calix[4]arenes modified by R2PO groups in upper or lower rim

被引:5
作者
Kryuchkova, Natalya A. [1 ]
Kostin, Gennadiy A. [1 ]
Korotaev, Evgeniy V. [1 ]
Kalinkin, Alexander V. [2 ]
机构
[1] Russian Acad Sci, Nikolacv Inst Inorgan Chem, Siberian Branch, Lavrentyev Av 3, RU-630090 Novosibirsk, Russia
[2] Russian Acad Sci, Boreskov Inst Catalysis, Siberian Branch, Lavrentyev Av 5, RU-630090 Novosibirsk, Russia
关键词
Calixarenes; Cobalt; Ruthenium; Complexes; X-ray photoelectron spectroscopy; Magnetochemical measurements; Quantum chemical calculations; DFT method; QTAIM method; METAL-COMPLEXES; EXTRACTION; CALIXARENE; DENSITY; IONS; APPROXIMATION; RECOGNITION; CO(II); CAVITY;
D O I
10.1016/j.elspec.2018.10.004
中图分类号
O433 [光谱学];
学科分类号
0703 ; 070302 ;
摘要
Interatomic interactions and charge state of atoms in calix[4]arenes functionalized by phosphoryl groups in the upper (L1) and lower (L2) rims, in complexes [Co-2(NO3)(4)*L1], [Co-2(NO3)(4)*L2] and in heterometallic comPlex [RuNO(NO2)(4)OH(H2O)Co*L2] have been studied with the methods of quantum chemistry, X-ray photoelectron spectroscopy and static magnetochemistry. According to the experimental and calculated data, the Co atoms are in the oxidation state 2+ for all compounds. The energies and shapes of the Ru(3p(3/2))-lines indicate formal oxidation states of Ru(II). Magnetic properties of investigated compounds are characterized by ferromagnetic interaction of high spin Co(II) atoms. Coordination of the Co(NO3)(2) fragments by the P = O-groups in the complexes leads to decreasing in the electron density on O and P atoms comparatively to L1 and L2.
引用
收藏
页码:114 / 123
页数:10
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