Structural Diversity of Zinc(II), Manganese(II), and Gadolinium(III) Coordination Polymers Based on Two Isomeric N-Heteroaromatic Polycarboxylate Ligands: Structures and Their Derived Mn₂O₃ for Lithium Storage Applications

Abstract

Tuning the coordination sites of two isomeric semirigid ligands, 5-(4-pyridin-3-yl-benzoylamino)isophthalic acid (3-H 2 PBI) and 5-(4-pyridin-4-yl-benzoylamino)isophthalic acid (4-H 2 PBI), afforded six new coordination polymers (CPs), Structural analysis shows that 1 consists of 2D honeycomb (6,3) net, three sets of networks interlace mutually, generating an unexpected 2D + 2D + 2D → 3D polycatenating interesting system. 2 exhibits a 3D pcu topology. 3 presents a unique 3D with 3,3,6T13 network topology. 4 possesses 3D 2-fold interpenetrated structure with rutile topology. 5 presents an alluring 2D architecture comprising two distinct topologies (kgd and hcb), stacked arrangement in an unexpected ABBABB mode. 6 displays 2D (4,4)-grid network. A differentiation of these structural features indicate that coordination connectivity of metals, together with binding modes of two ligands are accountable for the fascinating structural contrast. In addition, 2 and 5 were then transformed into Mn 2 O 3 via a simple heat treatment. Electrochemical test results show that both of the obtained Mn 2 O 3 moieties exhibit stable lithium storage properties and excellent rate capabilities.

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications

“…Harrowfield et al 81c). 223 Other similar wavy 2D structures of this kind have been reported. 522−527 448,533 This can be classified into three categories based on their orientation and way of catenation: (a) parallel/parallel, (b) diagonal/diagonal, and (c) parallel/diagonal (Scheme 2).…”

“…reported a chiral 2D MOF [(UO 2 ) 2 K 2 (C 7 ) 3 (H 2 O)]·0.5H 2 O with 8 2 .10 ( kla ) net topology based on a α,ω-dicarboxylic acid (C 7 = (HOOC-(CH 2 ) 5 -COOH)) showing parallel polycatenation between convoluted layers (Figure a,b) . Very recently, Deng and co-workers illustrated a Borromean type 2D to 3D polycatenation in [Zn­(3-PBI)­(H 2 O)] with hcb net topology and derived from a semirigid ligand 5-(4-pyridin-3-yl-benzoylamino)­isophthalic acid (3-H 2 PBI) (Figure c) . Other similar wavy 2D structures of this kind have been reported. − …”

“…The introduction of a free amine group demonstrated its ability to undergo intramolecular hydrogen bonding with bound anionic species due to which these are unapproachable to guest molecules. Apart from the aforesaid rhombic grid based 2D MOFs, several other examples are also reported. ,,,− …”

Structural Stability and Properties of Marokite-Type γ-Mn3O4

“…Synthetic manganese oxides and manganese oxide minerals play an important role in different technological processes and applications. , For example, some of them are utilized as effective catalysts, − as supercapacitors, as ferroelectrics or multiferroics, − as elements in ion batteries, − as semiconductors, and for many other purposes. − In general, manganese oxides, including Mn-based perovskites, − are inexpensive and highly functional materials, which combine interesting electronic and magnetic properties and, therefore, have remained in the focus of recent investigations.…”

Synthesis of Ilmenite-type ε-Mn2O3 and Its Properties

“…Manganese oxides display a range of unique physical and chemical properties and play an important role in basic sciences and in numerous industrial processes and devices. For instance, they are promising materials for applications in diverse magnetic technologies, − for catalysis, , for supercapacitor electrodes, for lithium storage and alkaline battery applications, − and for other goals. − Various Mn-rich oxides, such as manganite perovskites, A 1– x B x MnO 3 , more complex quadruple perovskites, for example, AMn 7 O 12 , − and many others, − demonstrate interesting and often industry-relevant characteristics. Hence, the synthesis of novel, chemically simple, inexpensive, and functional manganese oxides could uncover yet unknown scientific and industrial potentials.…”