Crystal growth and structural remarks on malonate-based lanthanide coordination polymers

Abstract

The synthesis, structural and thermal studies of several malonate-containing lanthanide(iii) complexes plus a structural overview of twenty-three known homometallic Ln(iii)-malonate systems are provided herein.

Synthesis, Thermal, Structural Analyses, and Photoluminescent Properties of a New Family of Malonate-Containing Lanthanide(III) Coordination Polymers

“…In the DSC plot an endotherm at about 150°C corresponds to the dehydration step, while the exotherms at about 300 and 410°C represent the combustion of the malonate ligands. The shapes of the TGA curves for 1 – 5 are similar to those of the other malonate-containing Ln 3+ complexes described in the literature (Muraishi et al, 1991; Doreswamy et al, 2003; Chrysomallidou et al, 2010; Delgado et al, 2016) suggesting that the stability of the complexes is comparable to the reported ones.…”

“…Lanthanide(III) ions are hard Lewis acids and prefer to combine with hard Lewis bases such as oxygen donors (Bünzli, 2014). On the basis of this fact, carboxylate ligands have been widely applied for the preparation of lanthanide coordination polymers (Hansson, 1973a,b; Wenmei et al, 1992; Marrot and Trombe, 1994; Benmerad et al, 2000; Hernández-Molina et al, 2000, 2002, 2003; Doreswamy et al, 2003, 2005; Thirumurugan and Natarajan, 2004; Cui et al, 2005; Yan et al, 2005; Cañadillas-Delgado et al, 2006; Deacon et al, 2006; Rahahlia et al, 2007; Zhang et al, 2007; Fang et al, 2008; Wang et al, 2009; Chrysomallidou et al, 2010; Silva et al, 2010; Jin et al, 2012; Seidel et al, 2012; Sharif et al, 2012; Calahorro et al, 2013; Tian et al, 2013; Bünzli, 2014; Delgado et al, 2016; Li et al, 2017). The flexible aliphatic dicarboxylates (e.g., malonate and succinate) are more fascinating than the rigid mono or aromatic carboxylates due to many possible conformations (Cui et al, 2005; Rahahlia et al, 2007; Wang et al, 2009; Delgado et al, 2016).…”

“…It can coordinate as a monodentate, bridging, and chelating ligand in monoanionic (hydrogen malonate, C 3 H 3 O4-) or dianionic (malonate, C 3 H 2 O42-) form (Rodríguez-Martín et al, 2002; Delgado et al, 2016). A number of reports have been published on the synthesis and structures of malonate-containing lanthanide polymers, which describe the versatility of the bonding modes of the malonate group (Hansson, 1973a,b; Wenmei et al, 1992; Marrot and Trombe, 1994; Benmerad et al, 2000; Hernández-Molina et al, 2000, 2002, 2003; Doreswamy et al, 2005; Cañadillas-Delgado et al, 2006; Zhang et al, 2007; Fang et al, 2008; Chrysomallidou et al, 2010; Silva et al, 2010; Jin et al, 2012; Delgado et al, 2016). Delgado et al reported a detailed overview on the crystal structures and topologies of these systems, as well as the molecular structures assembled by hydrogen-bonding from low-dimensional entities to higher-dimensional supramolecular architectures.…”

“…Delgado et al reported a detailed overview on the crystal structures and topologies of these systems, as well as the molecular structures assembled by hydrogen-bonding from low-dimensional entities to higher-dimensional supramolecular architectures. The study describes that most of the Ln 3+ -malonate (mal 2− ) complexes exist as dinuclear species (Delgado et al, 2016), while the reports about the mononuclear complexes are rare (Wenmei et al, 1992; Marrot and Trombe, 1994; Chrysomallidou et al, 2010; Silva et al, 2010).…”

Synthesis, crystal structures and, magnetic and photoluminescence properties of lanthanide-based metal–organic frameworks constructed with 2,5-dihydroxybenzene-1,4-dicarboxylic acid

“…2,3,10,16,[33][34][35] Lanthanide(III) ions have high affinity towards hard bases, such as oxygen donors and in this respect multicarboxylate ligands, which possess hard base sites of high density, seem to be ideal ligands in the construction of MOFs. [3][4][5]8,11,15,16,[34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] Among these ligands, the rigid carboxylates, benzene-1,4-dicarboxylic acid (Bdc-H 2 ) 4, [34][35][36][37][38] and its derivatives with a centrosymmetric structure 3,5,9,35,[38][39][40][41][42][43] have drawn considerable attention because they possess various coordination modes such as, monodentate, bis-monodentate, bidentate, tridentate and chelating bridging; which favor the bui...…”