Vibrational properties and bonding analysis of copper hexacyanoferrate complexes in solid state

J. Mink, A. Stirling, Dickson O. Ojwang, Gunnar Svensson, J. Mihály, Csaba Németh, Markus Drees, Laszlo Hajba

Research output: Contribution to journalReview article

2 Citations (Scopus)

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 Fm (Formula presented.) m (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.

Original languageEnglish
Pages (from-to)369-424
Number of pages56
JournalApplied Spectroscopy Reviews
Volume54
Issue number5
DOIs
Publication statusPublished - May 28 2019

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Copper
solid state
copper
Density functional theory
Chemical analysis
Water
Coordination Complexes
Vibrational spectra
density functional theory
Metal complexes
Software packages
Transition metals
Hydrogen
Ions
vibrational spectra
water
Crystalline materials
Molecules
transition metals
analogs

Keywords

  • factor group analysis
  • far-infrared spectroscopy
  • force constant calculations
  • Infrared spectroscopy
  • Raman spectroscopy
  • unit cell DFT calculation

ASJC Scopus subject areas

  • Instrumentation
  • Spectroscopy

Cite this

Vibrational properties and bonding analysis of copper hexacyanoferrate complexes in solid state. / Mink, J.; Stirling, A.; Ojwang, Dickson O.; Svensson, Gunnar; Mihály, J.; Németh, Csaba; Drees, Markus; Hajba, Laszlo.

In: Applied Spectroscopy Reviews, Vol. 54, No. 5, 28.05.2019, p. 369-424.

Research output: Contribution to journalReview article

Mink, J. ; Stirling, A. ; Ojwang, Dickson O. ; Svensson, Gunnar ; Mihály, J. ; Németh, Csaba ; Drees, Markus ; Hajba, Laszlo. / Vibrational properties and bonding analysis of copper hexacyanoferrate complexes in solid state. In: Applied Spectroscopy Reviews. 2019 ; Vol. 54, No. 5. pp. 369-424.
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AU - Ojwang, Dickson O.

AU - Svensson, Gunnar

AU - Mihály, J.

AU - Németh, Csaba

AU - Drees, Markus

AU - Hajba, Laszlo

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N2 - 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 Fm (Formula presented.) m (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.

AB - 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 Fm (Formula presented.) m (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.

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