Structural Study of Hydrated/Dehydrated Manganese Thiophene-2,5-diphosphonate Metal Organic Frameworks, Mn₂(O₃P–C₄H₂S–PO₃)·2H₂O

Abstract

Synthesis of thiophene-2,5-diphosphonic acid 2 is reported, and its use for synthesis of the original pristine materials Mn(2)(O(3)P-C(4)H(2)S-PO(3))·2H(2)O 3 is reported. The structure of material 3 has been fully resolved from single-crystal X-ray diffraction. Mn(2)(O(3)P-C(4)H(2)S-PO(3))·2H(2)O 3 crystallizes in a monoclinic cell (space group P2) with the following parameters: a = 11.60(1) Å, b = 4.943(5) Å, c = 19.614(13) Å, β = 107.22°. A noticeable feature of the structure of compound 3 is the orientation of the thiophene heterocycles that adopt two different orientations in two successive layers (along c). Thermal analysis of compound 3 indicates that the water molecules are easily removed from 160 to 230 °C while the dehydrated structure is stable up to 500 °C. The dehydrated compound obtained from 3 can be rehydrated to give the polymorphic compound Mn(2)(O(3)P-C(4)H(2)S-PO(3))·2H(2)O 4, which crystallizes in an orthorhombic cell (space group Pnam) with the following parameters: a = 7.5359(3) Å, b = 7.5524(3) Å, c = 18.3050(9) Å. The main difference between the structures of 3 and 4 arises from both the orientation of the thiophene rings (herringbone-type organization in 4) and the structure of the inorganic layers. The thiophene-2,5-diphosphonic acid moieties engaged in materials 3 and 4 adopt a different orientation likely due to rotation around the P-C bonds and via the dehydrated state 5, which is likely more flexible than the hydrated states. Study of the magnetic properties performed on compound 3 and 4 and on the dehydrated compounds Mn(2)(O(3)P-C(4)H(2)S-PO(3)) 5 complemented by the structural study has permitted us to characterize the antiferromagnetic ground state of sample 3, a weak ferromagnetic component in sample 4, and complete paramagnetic behavior in sample 5.

Silver-Based Hybrid Materials from meta- or para-Phosphonobenzoic Acid: Influence of the Topology on Silver Release in Water

“…32 This work was carried out within a context that aimed to study that aimed to examine the use of rigid phosphonic acid derivatives 33 , 34 as building blocks for the construction of crystalline hybrids under hydrothermal conditions to produce fluorescent, 35 thermally stable 36 and non-centrosymmetic materials. 37,38 For Through the study of the construction synthesis of silver-based hybrids we produced materials were produced with which couldthe potentially of acting as a reservoir of silver ions i.e. theyat could, via a disassembling of the hybrid in an aqueous media, exhibit bactericidal properties.…”

Hydrothermal synthesis for new multifunctional materials: A few examples of phosphates and phosphonate-based hybrid materials

“…In the case of metallophosphonate type materials, the shape and geometry of the organic molecule bonded to the PO 3 C tetrahedra play a crucial role in the design and the properties of the hybrid materials. Indeed, the organic part can (i) act as a linker to connect the organic network with the inorganic one, (ii) introduce some properties like luminescence or proton conductivity, and (iii) govern the rigidity, crystallinity, thermal stability and topology of the material induced by the presence of a rigid scaffold, such as aromatic cycles, [30] or flexible parts such as aliphatic chains [31]. All these parameters impact the final crystallinity of the hybrid materials that can be isolated, especially when hydrothermal conditions are used, as single crystals [32] or well crystallized powder [33].…”

“…Difference between the room temperature X-ray powder diffraction patterns (in a small[27][28][29][30][31] selected 2θ range) of α and β-NH 4 Fe 2 (PO 4 ) 2 (black and blue normalized patterns, respectively, λ Cu-Kα ). Inset: scanning electron microscope images of both samples showing size and morphology of the crystals.…”

Layered Simple Hydroxides Functionalized by Fluorene‐Phosphonic Acids: Synthesis, Interface Theoretical Insights, and Magnetoelectric Effect

“…The X n− anion located in the interlayer space may be substituted by a large variety of molecules via anionic exchange reaction. [45] The rigidity results from a direct connection of the phosphonic acid on an aromatic [46] or heteroaromatic ring [47] acting as a rigid molecular platform. As for the related compounds layered double hydroxides, [M 1-x 2+ M' x 3+ (OH) 2 ] x+ (X n− ) x/n .mH 2 O without anchoring of X − anions onto the layers, only a few works on the intercalation of molecules bearing phosphonic acids have been reported.…”

“…As for the related compounds layered double hydroxides, [M 1-x 2+ M' x 3+ (OH) 2 ] x+ (X n− ) x/n .mH 2 O without anchoring of X − anions onto the layers, only a few works on the intercalation of molecules bearing phosphonic acids have been reported. [47] These earliest results motivated the further exploration of diphosphonic acids as precursors of hybrid materials. [43] Over the recent years, efforts were made on the use of rigid phosphonic acids for the solvothermal one-pot synthesis of hybrid compounds, [44] with the aim to assess the consequences of this rigidity on the topology of the obtained systems.…”