Self-assembly and decay of Mn(ii) pivalate–phosphonate complexes

Abstract

A series of new manganese(II) pivalate-phosphonate complexes with various nuclearities (Mn 4 , Mn 10 , and Mn 20 ) under aerobic conditions was synthesized by self-assembly of simple reagents. The constitution of polynuclear architectures is affected by the reaction temperature. The structures of the complexes were determined by single crystal X-ray analysis. Magnetic behavior of the compounds points to dominant antiferromagnetic exchange interactions. Antiferromagnetic coupling with J Mn-Mn = À0.097(1) cm À1 , g Mn = 1.993(1) for an equilateral tetrahedron model simulates the magnetic behavior of the tetranuclear complex Mn 4 with a cube-like core.

Molecular Metal Phosphonates

“…Interestingly, heating the decanuclear compound at 80°C afforded an icosanuclear Mn II phosphonate cluster, [(HPiv) 8 8 Mn 20 4 (μ 3 -Piv) 2 (μ-Piv) 10 ]. 182 A heterometallic 3d−4f decanuclear Mn II containing phosphonate cage, [Mn II 4 Gd III 6 (O 3 PCH 2 Ph) 6 (HO 2 CBut) 13 …”

“…The core of this complex has a distorted cube type shape ( Figure 58). 182 Alternate vertices of the cubic core are occupied by phosphorus and manganese atoms. This structural type is quite common and has been found in other transition metal and main-group metal phosphonates and phosphates.…”

“…As mentioned above, the nuclearity of Mn II phosphonates varies from 1 to 20. 182 54). 183 In this compound, Mn II has in its coordination periphery two 1,10-phenanthroline and two monodentate [t-BuPO 3 H] − ligands.…”

“…195 As mentioned above, the reaction of MnCl 2 •4H 2 O, t-BuPO 3 H 2 , and NaPiv afforded the tetranuclear derivative [(HPiv) 12 Mn 4 (μ 3 -O 3 PBu-t) 4 ]. 182 Decreasing the temperature from 98 to 30 °C resulted in the formation of the decanuclear Mn II phosphonate, [(HPiv) 8 Mn 10 (μ-Cl) 4 (μ 5 ,η 2 -O 3 PBu-t) 4 (μ-Piv) 8 ] (Figure 59). 182 The decanuclear cage is constructed by multiple coordination action of the μ-Cl, μ-Piv, and [t-BuPO 3 ] 2− ligands.…”

Nanoporous Metal Phosphonate Hybrid Materials as a Novel Platform for Emerging Applications: A Critical Review

“…[67] In addition, the ordered mesostructures could only be reserved for small mesopore sizes, [67] therefore underscoring the urgency of novel strategies. As a great option, nanocrystal self-assembly, which usually involves noncovalent or weak covalent interactions for changing the disordered morphologies of materials into ordered ones, has been developed to control the well-defined pore structure and desired properties of metal phosphonate hybrids, [68][69][70][71][72][73][74][75][76][77][78] as summarized in Table 3. This template-free self-assembly synthesis process is usually initiated by a self-assembly procedure from interactions between the precursor molecules and subsequently runs the ordered attachment for the generation of porous nanostructures.…”