Issue 47, 2024

A family of luminescent heterometallic coordination polymers based on lanthanide(iii) ions and 6-methyl-2-oxonicotinate: near-infrared/visible emitters and colour fine-tuning

Abstract

The work presented herein reports on the synthesis, structural and physicochemical characterization and luminescence properties of a family of isostructural coordination polymers (CPs) with a general formula {[Ln(6m2onic)4Na(H2O)3]·8H2O}n (where Ln(III) = Nd (1Nd), Sm (2Sm), Dy (3Dy), Er (4Er), Tm (5Tm), Yb (6Yb) and Dy0.77Eu0.12Y0.11 for the multi-metal compound (7DyEuY) and 6m2onic = 6-methyl-2-oxonicotinate). The crystal structures consist of one-dimensional heterometallic arrays where octacoordinated lanthanide and hexacoordinated sodium centres are sequentially linked and which are held together into a 3D architecture by an extensive hydrogen bonding network formed by the crystallisation water molecules. Photoluminescence measurements in the solid state at variable temperature reveal good properties based on the capacity of the 6m2onic ligand to provide ligand-centred excitation, as suggested by time-dependent density functional theory (TDDFT), and promote efficient energy transfers to the lanthanide(III) ions, to eventually present intense emissions in both the visible and near-infrared (NIR) regions. On the one hand, compound 4Er displays characteristic lanthanide-centred bands in the NIR region even at room temperature, meaning that the framework is able to isolate the excitons from the vibrational quenching component. On the other hand, regarding the compounds emitting in the visible region, the almost white light emitted by compound 3Dy with a quantum yield (QY) of 6.2% should be noted. Both a purer white emission and an improved QY (up to 15.8%) may be achieved by means of a doping strategy of europium and yttrium ions into the Dy counterpart. Finally, taking advantage of white light emitted by compound 3Dy, the chemical and optical stabilities in water have been confirmed by the photophysical study performed in solution.

Graphical abstract: A family of luminescent heterometallic coordination polymers based on lanthanide(iii) ions and 6-methyl-2-oxonicotinate: near-infrared/visible emitters and colour fine-tuning

Supplementary files

Article information

Article type
Paper
Submitted
02 Sep 2024
Accepted
25 Oct 2024
First published
15 Nov 2024
This article is Open Access
Creative Commons BY-NC license

CrystEngComm, 2024,26, 6707-6718

A family of luminescent heterometallic coordination polymers based on lanthanide(III) ions and 6-methyl-2-oxonicotinate: near-infrared/visible emitters and colour fine-tuning

L. Razquin-Bobillo, J. A. García, R. Hernández, A. Rodríguez-Diéguez and J. Cepeda, CrystEngComm, 2024, 26, 6707 DOI: 10.1039/D4CE00881B

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