Interplane Distances Modulation in Lanthanide-Based Coordination Polymers

Abstract

We present here two new materials, Er 2 (BDC) 3 (H 2 O) 6 (1) and Er 2 (NDC) 3 (H 2 O) 6 (2), where BDC stands for 1,4-benzenedicarboxylate and NDC stands for 2,6-naphthalenedicarboxylate ligand. In addition to their compositions, both structures adopt the same general arrangement: that is, a succession, along the c b-axis, of erbium atoms planes and organic spacers-ligands planes. The longer naphthalene derivative ligand increases the c parameter, but the organization inside the erbium cations planes is kept, including the nature and the geometry of the coordination spheres of the lanthanide ions, the number and the repartition of the water molecules, and the network of hydrogen bonding. The chemical nature, the flexibility, and the topology of the organic ligands allow the preservation of the organic-inorganic interface within the materials. This study clearly shows the opportunity to imagine new lanthanide-based materials with the tools of crystal engineering.

A family of lanthanide-containing molecular open frameworks with high porosity: [Ln(abdc)(Habdc), nH2O]∞ with Ln=La–Eu and 8⩽n⩽11

“…Therefore, for more than 10 years we are developing a green synthetic strategy [33] implying water as solvent, non-toxic reagents, high yield reactions conducted at ambient temperature and pressure and gel media for crystal growth [34]. These requirements have led us to synthesize numerous lanthanide containing coordination polymers involving benzene-poly-carboxylate ligands [23,25,29,[34][35][36][37][38][39]. Actually, benzene-poly-carboxylate ligands have drawn much attention because they are chemically and thermally stable, present a structuring effect thanks to p-stacking, and carboxylato functional groups allow one to expect a structural diversity due to their numerous possible coordination modes [40].…”

Synthesis, spectroscopic and thermal studies of 2,3-naphthalenedicarboxylates of rare earth elements

“…In constructing coordination polymers, aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid [11,12], 2,6-naphthalenedicarboxylic acid [13][14][15][16] and one of the asymmetrical benzenedicarboxylic acids, 1,2-benzenedicarboxylic acid [17][18][19][20], are used extensively in the synthesis of coordination polymers with lanthanide ions. In particular, dicarboxylate of benzene or naphthalene, with different coordination preferences, offers many advantages in the construction of highly porous and robust metalorganic frameworks [21,22].…”

Facile access to efficiently luminescent Ln3+ phosphonic ester coordination polymers (Ln = Eu, Tb, Dy)

“…[1][2][3] In recent years coordination polymers turned out to be a suitable scaffold for accommodating isolated lanthanide centers. [4][5][6] While the most frequently employed binding sites in coordination polymers or metal-organic frameworks are carboxylates or nitrogen bases, 7,8 phosphonates 9, 10 and organophosphates have been used as ligands as well. 11 By contrast, the use of phosphonic esters for this purpose is less explored and just started to emerge.…”