期刊
INORGANIC CHEMISTRY
卷 52, 期 13, 页码 7508-7523出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic400422d
关键词
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资金
- University Grants Commission (UGC), New Delhi [UGC/748/Jr]
- Council of Scientific and Industrial Research (CSIR), New Delhi [09/028. (0732)/2008-EMR-I]
- DST-FIST, India
- DGICYT of Spain [CTQ2011-27512/BQU, CONSOL-IDER INGENIO CSD2010-00065]
- Direccio General de Recerca i Innovacio del Govern Balear [23/2011]
- DST [SR/S1/PC-57/2008]
- CSIR [21(0871)/11/EMR-II]
Five heterobimetallic copper(II) uranium(V1) complexes [(CuL1)-UO2(NO3)(2)] (1), [{CoL1(CH3CN)}UO2(NO3)(2)] (2), [{CuL1(CH3COCH3)}UO2(NO3)(2)] (3), [{CUL2(CH3CN)}UO2(NO3)(2)] (4), and [{CuL2(CH3COCH3)}UO2(NO3)(2)][{CuL2}UO2(NO3)(2)] (5) have been synthesized by reacting the Cu(II)derived metalloligands [CUL1] and [CuL2] (where, H2L1 = N,N'-bis(a-methylsalicylidene)-1,3-propanediamine and H2L2 = N,N'-bis(salicylidene)-1,3-propanediamine) with UO2(NO3)(2)center dot 6H(2)O in 1:1 ratio by varying the reaction temperature and solvents. oi Absorption and fluorescence quenching experiments (steady-state and time-resolved) indicate the formation of 1:1 ground-state charge transfer copper(II)-uranium(V1) complexes in solution. X-ray single-crystal structure reveals that each complex contains diphenoxido bridged Cu(II) U(VI) &nuclear core with two chelated nitrato coligands The complexes are solvated (acetonitrile or acetone) in the axial position of the Cu(II) in different manner or desolvated. The supramolecular interactions that depend upon the coordinating inetalloligands seem to control the so vation. In complexes 2 and 3 a 'rare NO3-center dot center dot center dot NO3- weak interaction plays an important role in forming supramolecular network whereas an uncommon U=O center dot center dot center dot NO3- weak interaction helps to self-assemble heterobinuclear units in complex 5. The significance of the noncovalent interactions in terms of energies and geometries has been analyzed using theoretical calculations.
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