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本文合成了一系列稀土叔铵盐配合物[(C_4H_9)_3NH]_3·[Ln(NO_3)_6],其中Ln=La、Ce、Pr、Nd。研究了该系列配合物的中红外光谱以及热谱;测定了其在乙醇溶液中的摩尔电导率,证明其属于3:1型电解质。用四圆衍射仪测定了[(C_4H_9)_3NH]_3·[La(NO_3)_6]的晶体结构。该晶体属单斜晶系,C_2空间群。晶胞参数:a=1.4983nm;b=1.6715nm;c=1.1131nm;β=91.82°,Z=2。中心离子镧被来自六个硝酸根的十二个氧原子所配位,配位数为12。La-O平均键长为0.2659nm。其配位多面体为扭曲的双交错式3333堆积结构的二十面体。用INDO程序计算了[k(No_3)_6]_3-的电子结构,结果表明:中心离子镧主要是以5d轨道与氧原子成键的,而4f轨道则不参与化学键的形成。
In this paper, a series of rare earth tertiary ammonium salt complexes [(C_4H_9) _3NH] _3 [Ln (NO_3) _6] were synthesized, in which Ln = La, Ce, Pr and Nd. The mid-IR spectra and thermospectroscopy of the complexes were investigated. The molar conductivity of the complexes in ethanol solution was determined, which is proved to be a 3: 1 type electrolyte. The crystal structure of [(C_4H_9) _3NH] _3 · [La (NO_3) _6] was measured by a four-circle diffractometer. The crystal is monoclinic, C_2 space group. Cell parameters: a = 1.4983 nm; b = 1.6715 nm; c = 1.1131 nm; β = 91.82 °, Z = 2. The central ion, lanthanum, is coordinated by twelve oxygen atoms from six nitrates with a coordination number of 12. The average bond length of La-O is 0.2659nm. The coordination polyhedron is a twisted icosahedron with a double interleaved 3333 stacking structure. The electronic structure of [k (No_3) _6] _3- was calculated by INDO program. The results show that the central ion lanthanum mainly bonds to the oxygen atom in the 5d orbit, while the 4f orbitals do not participate in the chemical bond formation.