Mild Hydrothermal Synthesis and Structural Determination of Two Layered, Structurally Related Inorganic–Organic Hybrid Vanadates with Nickel(II) and Tris(2‐aminoethyl)amine

Abstract

2D Ni2(C6H19N4)2(V6O18)·2H2O (1) and Ni2(C6H19N4)2(V6O18)·H2O (2) are inorganic–organic hybrid compounds that have been synthesised under hydrothermal conditions. Crystalline aggregates composed of both compounds were obtained and structural characterisation was subsequently carried out using single crystalline fragments of these aggregates. Optimisation of the synthetic conditions allowed us to obtain 1 as a polycrystalline powder. The crystal structures of 1 and 2 were solved using single‐crystal X‐ray diffraction data. Both compounds are structurally related, as the layers from which they are built have the same composition and connectivity in both structures. The main differences between them are the layer stacking and water contents. UV/Vis spectroscopy of 1 shows the characteristic features of the NiII d8 cation in slightly distorted octahedral symmetry. From the temperature‐dependent magnetic susceptibility measurements the parameter D/hc = –3.75 cm–1 was obtained. Phase 1 undergoes a reversible structural transformation at approximately 60 °C as a result of the dehydration process. This dehydration gives rise to a decrease in the unit cell volume.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Two 3D POM‐Based Inorganic–organic Hybrid Compounds Constructed from Different {VO3}4n Subunits and N‐donor ligands: Syntheses, Structures, Electrocatalytic and Magnetic Properties

“…Each vanadium center is coordinated by four O atoms in a tetrahedral coordination environment, while Cu ions in the asymmetry unit exhibiting trigonal bipyramid {CuN 2 O 3 } geometry, defined by two nitrogen atoms (N1, N4) from two bim ligands and three oxygen atoms (O3, O4, O6) from neighboring three VO 4 tetrahedra (Figure b). The bond lengths of V–O range from 1.610(3) to 1.796(2) Å and the O–V–O angles range from 107.31(11) to 111.34(12)°, which are consistent with previously reported vanadates . As shown in Figure , two types of parallel chains exist in the skeleton of 1 .…”

“…The bond lengths of V-O range from 1.610(3) to 1.796(2) and the O-V-O angles range from 107.31(11) to 111.34 (12)8, which are consistent with previously reported vanadates. [18][19][20] As shown in Figure 2 Besides, two kinds of heterometallic helical chains made up of -(V-O-Cu)-exist with opposite helicities along a axis (a lefthanded helix and a right-handed helix), as shown in Figure 3.…”

Vanadium Polyoxoanions within Coordination Polymers Based on a Macrocyclic Nickel Complex: Structural Diversities and Single‐Crystal to Single‐Crystal Transformation

“…As [NiL] 2+ in these polymers assumes only one coordination mode, the diverse structures of these coordination polymers originate from the structural diversity of the vanadium polyoxoanions, which are closely related to the pH of the reaction solution. To the best of our knowledge, the [V 16 O 42 ] n 4 n – sheet in 1 , [V 6 O 18 ] 6– ring in 2 , [VO 3 ] n n – chain in 3 , and [VO 3 ] n n – sheet in 4 have already been reported in the literature, , whereas the [V 10 O 29 ] n 8 n – chain in 5 is reported for the first time in this work . The results of this work reveal that vanadium polyoxoanions really can show diverse structures under slightly different synthetic conditions.…”

{Co(HBpe)2}(V4O12): pedal motion induced order–disorder P1̄→C1̄ transition and disrupted C1̄→C2/m displacive transition due to thermal instability

“…17 Although the hybrid materials are expected to exhibit improved properties and functions not seen in pure inorganic or organic phases, studies of their thermal properties are still rare. [18][19][20][21] For this reason in this work the structural changes due to the pedal motion of the HBpe ligand are studied by single crystal X-ray diffraction and powder diffraction. The thermal evolution of the cell parameters and crystal structures at different temperatures is discussed, pointing the effect of the pedal motion in the crystal structure.…”