Issue 35, 2014

Coordination polymers based on a glycine-derivative ligand

Abstract

The combination of the glycine-derivative supramolecular salt 4,6-bis(carboxymethylamino)-2-oxo-2,3-dihydro-1,3,5-triazin-1-ium chloride (H2bodt·HCl) and lanthanide(III) chloride hydrates under hydrothermal conditions (120 °C, 48 h) led to the formation of a family of isotypical materials formulated as [Ln(bodt)(Hbodt)] [where Ln3+ = La3+ (1), (La0.95Eu0.05)3+ (2) and (La0.95Tb0.05)3+ (3)]. The synthesis of the novel precursor H2bodt·HCl is detailed. The structures of H2bodt·HCl and its intermediate compound were unveiled by single-crystal X-ray diffraction and characterized by standard liquid-state techniques. The crystallographic details of compound 1 were unveiled in the monoclinic P2/c space group by using single-crystal X-ray diffraction, with the crystal structure of 1 comprising a one-dimensional 1[La(bodt)(Hbodt)] coordination polymer. All polymeric materials were fully characterized by FT-IR, electron microscopy (SEM and EDS), powder X-ray diffraction, and elemental and thermogravimetric analyses. The photoluminescent properties of 1 and of the mixed-lanthanide materials 2 and 3 were investigated at ambient and low temperatures. An excited-state intermolecular proton transfer (ESPT) process, induced by intermolecular hydrogen-bonding interactions, is proposed to account for the observed anomalous emission and excitation spectra of 1. Aiming at providing an in-depth understanding of the emission (fluorescence and phosphorescence) properties of the ligand, time-dependent density functional theory (TD-DFT) calculations were also performed.

Graphical abstract: Coordination polymers based on a glycine-derivative ligand

Supplementary files

Article information

Article type
Paper
Submitted
05 Mar 2014
Accepted
25 Mar 2014
First published
25 Mar 2014

CrystEngComm, 2014,16, 8119-8137

Author version available

Coordination polymers based on a glycine-derivative ligand

S. M. F. Vilela, D. Ananias, P. Silva, M. Nolasco, L. D. Carlos, V. de Zea Bermudez, J. Rocha, J. P. C. Tomé and F. A. Almeida Paz, CrystEngComm, 2014, 16, 8119 DOI: 10.1039/C4CE00465E

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