Synthesis, crystal structures and spectroscopic studies of praseodymium(III) malonate complexes

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

“…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).…”

“…The use of multidentate organic linkers together with the high coordination number of lanthanide ions help to construct diverse structural motifs with unexpected properties. The structural arrangements in the lanthanide dicarboxylate polymers range from one- (Yan et al, 2005; Chrysomallidou et al, 2010; Silva et al, 2010; Li et al, 2017), two- (Hernández-Molina et al, 2000; Cañadillas-Delgado et al, 2006; Li et al, 2017), to three-dimensional (Hansson, 1973a,b; Wenmei et al, 1992; Marrot and Trombe, 1994; Benmerad et al, 2000; Hernández-Molina et al, 2002, 2003; Doreswamy et al, 2003, 2005; Thirumurugan and Natarajan, 2004; Cañadillas-Delgado et al, 2006; Zhang et al, 2007; Fang et al, 2008; Chrysomallidou et al, 2010; Jin et al, 2012; Seidel et al, 2012; Calahorro et al, 2013) coordination networks. Malonic acid, C 3 H 4 O 4 , is a simple dicarboxylic acid that exhibits a rather flexible stereochemistry and a variety of coordination modes toward metal ions.…”

“…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).…”

Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me2mal)2} Fragment

“…Removal of 1‐c nodes leads to a 2,3,4,5‐c net, and replacing of 2‐c nodes in the net by edges gives a 3‐c ladder‐like underlying net with a topology of 1‐periodic Fischer spherical packing 4 4 (0,2) (Figure ). According to the TTO/TTD service of the ToposPro project the 4 4 (0,2) motif is a commonly observed topology and occurs in 3503 crystal structures including the six mal complexes (Table S1 in the Supporting Information) [La(mal) 2 (H 2 O) 2 ] · H 2 O, [Co(NH 3 ) 6 ][NpO 2 (mal) 2 ](Hmal) · H 2 O, [Co(NH 3 ) 6 ][NpO 2 (mal) 2 ]NO 3 · H 2 O, [Co(NH 3 ) 6 ][NpO 2 (mal) 2 ]OH · H 2 O, [Ce(mal)Cl(H 2 O) 3 ] · 0.5 H 2 O, and [Pr(mal)Cl(H 2 O) 3 ] · 0.5 H 2 O, as well as two complexes of other derivatives: [UO 2 (cbdc)] and [Na 2 (cpdc)(H 2 cpdc)(H 2 O) 4 ] (H 2 cpdc = cyclopropane‐1,1‐dicarboxylic acid) . However, these eight complexes differ from the 1 in their coordination formulas: AB 21 M 1 2 , AK 03 2 M 1 2 ,, , AK 03 M 1 4 ,, and AK 03 B 01 M 1 2 …”