0000000000342006
AUTHOR
Robert Podgajny
Humidity-Driven Reversible Transformation and Guest Inclusion in a Two-Dimensional Coordination Framework Tailored by Organic Polyamine Cation
Using a polyamine cation tetrenH55+ (tetren = tetraethylenepentaamine), we tailored the dynamic layered material (tetrenH5)1.6{CoII(H2O)2[MIV(CN)8]}4·xH2O (1, M = W, x = 12; 2, M = Mo, x = 11.2). 1 and 2 consist of strongly corrugated two-dimensional (2D) cyano-bridged monolayers {CoII(H2O)2[MIV(CN)8]}n2n– of square grid topology stacked in an alternate manner with cationic layers of tetrenH55+ and H2O molecules. The observed single-crystal-to-single-crystal (SCSC) transformation is due to the reversible dehydration of 1 and 2 to the respective monocrystalline materials (tetrenH5)1.6{CoII[MIV(CN)8]}4 (1deh and 2deh). Structural modifications consist of the change of coordination number (C.N…
Magneto-structural correlations in discrete $Mn^{II}‐W^V$ cyano‐bridged assemblies with polyimine ligands
We present the magneto-structural correlations for two novel discrete cyano-bridged assemblies based on cationic complexes of manganese(II) with diimine ligands and octacyanotungstate(V) ions. The crystal structure of [Mn II (terpy)(dmf)-(H 2 O) 2 ][Mn II (terpy)(H 2 O)(dmf)(μ-NC)W V (CN) 7 ] 2· 6H 2 O (1) (terpy = 2,2';6',2"-terpyridine, dmf = dimethylformamide) contains dinuclear {Mn II W V } - cyano-bridged anions, while the crystal structure of [Mn II (phen) 3 ] 2 [MnII(phen) 2 (μ-NC) 2 -W V (CN) 6 ] 2 (ClO 4 ) 2 ·9H 2 O (2) (phen = 1,10-phenanthroline) is built of tetranuclear {Mn II 2 W V 2} 2- square anions. Intramolecular Mn-W magnetic interactions through the cyano bridges are repr…
Magnetostructural correlations in CuII−NC−WV linkage: the case of [CuII(diimine)]2+−[WV(CN)8]3− 0D assemblies
International audience; We report on the syntheses, crystal structures, and magnetic properties of two cyano-bridged molecular assemblies: [CuII(phen)3]2{[CuII(phen)2]2[WV(CN)8]2}(ClO4)2·10H2O (phen = 1,10-phenanthroline) (1) and {[CuII(bpy)2]2[WV(CN)8]} {[CuII(bpy)2][WV(CN)8]}·4H2O (bpy = 2,2′-bipyridyl) (2). Compound 1 consists of cyano-bridged [CuII2WV2]2− molecular rectangles and isolated [CuII(phen)3]2+ complexes. The molecular structure of 2 reveals cyano-bridged trinuclear [CuII2WV]+ and dinuclear [CuIIWV]− ions. Magnetic interactions in 1 are interpreted in terms of the model of a tetranuclear moiety consisting of two ferromagnetic CuII−NC−WV units (J1 = +39(4) cm−1) interacting ant…
Three-dimensional bimetallic octacyanidometalates $[M^{IV}{(\mu-CN)_{4}Mn^{II}(H_{2}O)_2}_2 \cdot 4H_{2}O]_{n}$ (M=Nb,Mo,W) : synthesis, single-crystal X-ray diffraction and magnetism
Abstract We report the synthesis, the single-crystal X-ray crystallographic structures and the magnetic properties of three new isostructural cyanido-bridged networks: [M IV {(μ-CN) 4 Mn II (H 2 O) 2 } 2 ·4H 2 O] n [M IV = Nb IV ( 1 ), Mo IV ( 2 ), W IV ( 3 )]. For compound 1 , the magnetic properties reveal a ferrimagnetic phase below 50 K. In contrast, compounds 2 and 3 show a paramagnetic behaviour with no magnetic ordering down to 2 K. The only electronic difference between the two kinds of compounds is the presence of two paired electrons on Mo IV ( 2 ) and W IV ( 3 ) (d 2 electronic configuration, S = 0) with no possible exchange interactions with Mn II ions (d 5 electronic configur…