A Study of Several Mixed Cationic Systems of (Pr/La)Co(CN)6·5H2O

Direct Evidence for O−H···NC Hydrogen Bonding in a Cyanide-Bridged Lanthanide−Transition-Metal Complex (H2O)6(DMF)6Ho2[Ni(CN)4]3: An Eight-Coordinated Holmium Center with a Bicapped (Square Face) Trigonal Prismatic Geometry

“…Mullica et al, Hulliger et al, and others − reported structure determinations of a series of cyanide-bridged lanthanide−transition-metal hydrates that are extended arrays, whereas we have reported several structures of the H 2 O-free cyanide-bridged lanthanide−transition-metal arrays. ,13c There are two published results in which multiple H 2 O and N , N -dimethylformamide (DMF) ligands were both present in the lanthanide coordination spheres. , Unlike the systems in which extended network structures are observed, these complexes exist as oligomers containing two lanthanide and three transition-metal atoms. It appears that the number of ligating water molecules in the lanthanide coordination sphere influences the formation of the network structure, which in turn is critical for achieving long-range magnetic ordering at a finite temperature …”

“…The C−N bond distances range from 1.140(6) to 1.157(6) Å. The Ho−NC interaction is ionic . The two Ho−N−C angles are 157.9(4) and 170.8(4)°.…”

“…There has been continued interest in cyanide-bridged lanthanide−transition-metal complexes because of their applications as precursors in the preparation of rare earth orthoferrites (perovskite-type oxides), oxide fuel cells, electroceramic materials, , and chemical sensor materials; in the preparation of fluorescent materials and zeolitic-type materials; , in high-pressure tunable nonradiative energy-transfer processes; as semipermeable solid membranes in reverse osmosis desalination of seawater; , as the catalysts in carbonylation reactions and chiral selective ring-opening reactions; in the medical treatment of heavy-metal poisoning and the environmental cleanup of radioactive materials and heavy metals; and in analytical ion-exchange columns for selective metal separation …”

Negative Thermal Expansion in LnCo(CN)6 (Ln=La, Pr, Sm, Ho, Lu, Y): Mechanisms and Compositional Trends

“…The linear trend seen here contrasts with the more complex behavior for divalent transition‐metal substitution in M II Pt IV (CN) 6 (M=Mn, Fe, Co, Ni, Cu, Zn, Cd), for which the magnitude of NTE follows the Irving–Williams series of complex stability owing to the influence of crystal‐field stabilization energies on M II N bond strength and for which Jahn–Teller effects are present;11 for LnCo(CN) 6 the absence of significant crystal field effects in the essentially spherical Ln III ions yields fine, continuous control over thermal expansivities by metal substitution. A possible method for finer tuning of the NTE is to employ mixed‐lanthanoid solid‐solution phases,14 which are expected to possess CTEs between those of the single‐lanthanoid phases.…”

Synthesis, structure and magnetic property of [Ce(DMSO)2(H2O)Fe(CN)6]

“…Due to the extensive applications in preparing magnetic materials, chemical sensor materials, fluorescent materials, zeolitic-type materials, and so forth, cyanide-bridged lanthanide-transition metal complexes have attracted continuous interest for about two decades [1][2][3][4][5][6][7]. Most of the known cyanide-bridged lanthanide-transition metal complexes contain such ligands as DMF, urea and caprolactam, while DMSO is not common.…”