ABSTRACT Vibrational spectroscopic study of crystalline copper hexacyanoferrate complexes of composition K4CuII6 [FeII(CN)6]4·nH2O (1) and CuII6[FeIII(CN)6]4·nH2O (2) with -Cu-N≡C-Fe- bridging structures have been performed. The cubic Fmm (Oh5) unit-cells contain ideally 4 Fe and 4 Cu ions which were calculated by periodic density functional theory (DFT) (using the Gaussian09 C.01 software package) for ideal lattice compositions of K8CuII4[FeII(CN)6]4 (1a), K4CuII4[FeIII(CN)6]4 (2a) and with lattice water molecules KCuII4[FeIII(CN)6]3·6H2O (3a). Systematically, non-linear Cu-N≡C structure was fitted with Cu-N≡C bond angles about 155° for complexes 1a, 2a, and 3a. Practically, all optically active internal modes of Fe(CN6)n− moieties resulted from factor group analysis as 4A1g + 6Eg + 4F1g + 10F1u were experimentally observed and assigned. Some low-frequency translatory and librational modes were also interpreted. Vibrational bands were assigned to cis- and trans-Cu(NC)4(OH2) complexes which are formed in the lattice holes of both complexes. Vibrational spectra and force constants of a great number of transition metal hexacyano complexes of compositions K4[MII(CN)6], K3[MIII(CN)6], CsLi2[MIII(CN)6] and Prussian blue analogues have been reexamined and recalculated. Internal and external modes of 6 different lattice water species (coordinated, hydrogen bonded, or zeolitic type) have been interpreted for complex 2 using results of periodic DFT calculation of model complex 3a.

中文翻译：

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固态六氰基铁酸铜配合物的振动特性及键合分析

摘要 组成 K4CuII6 [FeII(CN)6]4·nH2O (1) 和 CuII6[FeIII(CN)6]4·nH2O (2) 与 -Cu-N≡C-Fe- 的结晶六氰基铁酸铜配合物的振动光谱研究已经进行了桥接结构。立方 Fmm (Oh5) 晶胞理想情况下包含 4 个 Fe 和 4 个 Cu 离子，这些离子通过周期密度泛函理论 (DFT)（使用 Gaussian09 C.01 软件包）计算得出，用于 ​​K8CuII4[FeII(CN)6 的理想晶格组成]4 (1a), K4CuII4[FeIII(CN)6]4 (2a) 和晶格水分子 KCuII4[FeIII(CN)6]3·6H2O (3a)。系统地，非线性 Cu-N≡C 结构与复合物 1a、2a 和 3a 的 Cu-N≡C 键角约为 155°。实际上，Fe(CN6)n− 部分的所有光学活性内部模式均由因子组分析产生，如 4A1g + 6Eg + 4F1g + 10F1u 被实验观察和分配。还解释了一些低频平移和振动模式。振动带被指定为顺式和反式 Cu(NC)4(OH2) 配合物，它们在两种配合物的晶格孔中形成。重新研究了大量由 K4[MII(CN)6]、K3[MIII(CN)6]、CsLi2[MIII(CN)6] 和普鲁士蓝类似物组成的过渡金属六氰基配合物的振动谱和力常数。重新计算。已经使用模型复合物 3a 的周期性 DFT 计算结果解释了复合物 2 的 6 种不同晶格水物质（配位、氢键或沸石型）的内部和外部模式。重新研究了大量由 K4[MII(CN)6]、K3[MIII(CN)6]、CsLi2[MIII(CN)6] 和普鲁士蓝类似物组成的过渡金属六氰基配合物的振动谱和力常数。重新计算。已经使用模型复合物 3a 的周期性 DFT 计算结果解释了复合物 2 的 6 种不同晶格水物质（配位、氢键或沸石型）的内部和外部模式。重新研究了大量由 K4[MII(CN)6]、K3[MIII(CN)6]、CsLi2[MIII(CN)6] 和普鲁士蓝类似物组成的过渡金属六氰基配合物的振动谱和力常数。重新计算。已经使用模型复合物 3a 的周期性 DFT 计算结果解释了复合物 2 的 6 种不同晶格水物质（配位、氢键或沸石型）的内部和外部模式。