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合成了标题所示的双核铜配合物,并以红外光谱,电子光谱,电导和元素分析进行了表征,9种化合物的ESR谱表明g_∥>g_⊥,故均为典型的Cu(Ⅱ)四方配位,配体σ-BMPD的配合物[Cu_2(σ-BMPD)X_m]·X_n·xH_2O(X表示NO_3~-,Cl~-,ClO_4~-;m=1,2,4,n=0,2,3;x=0,5,6)的ESR在g_∥区域有7重峰的超精细结构。[Cu_2(p-BMPD)(ClO_4)_2](ClO_4)_2则在g_⊥区域有窄的超精细分裂,表明配体的氮存在。在DMF溶液中,用环伏安法研究了配合物的电化学性质,9种配合物均为准可逆电子转移过程,并测定了它们的氧化还原电势。σ-BMPD配合物为2步1电子转移过程,而m-BMPD和p-BMPD配合物则表现为2个连续1电子转移过程在同一电位。
The binuclear copper complexes shown in the title were synthesized and characterized by FTIR, electron spectroscopy, conductivity and elemental analysis. The ESR spectra of nine compounds showed that g_∥> g_⊥, Coordination ligands, the ligand σ-BMPD complex [Cu_2 (σ-BMPD) X_m] · X_n · xH_2O (X represents NO_3 ~ -, Cl ~ -, ClO_4 ~; m = 1,2,4, n = 0 , 2, 3; x = 0,5,6) has a hyperfine structure with a 7-fold ESR in the g_ // region. The [Cu_2 (p-BMPD) (ClO_4) _2] (ClO_4) _2 has a narrow hyperfine division in the g_⊥ region, indicating the presence of nitrogen in the ligand. The electrochemical properties of the complexes were investigated by cyclic voltammetry in DMF solution. All nine complexes were quasi-reversible electron transfer and their redox potentials were determined. The σ-BMPD complex is a 2-step 1 electron transfer process, whereas the m-BMPD and p-BMPD complexes exhibit 2 consecutive 1-electron transfer processes at the same potential.