Turning 3D Covalent Organic Frameworks into Luminescent Ratiometric Temperature Sensors

Laurens Bourda; Anna M Kaczmarek; Min Peng; Sonali Mohanty; Hannes Rijckaert; Pascal Van Der Voort; Kristof Van Hecke

doi:10.1021/acsami.3c07544

Turning 3D Covalent Organic Frameworks into Luminescent Ratiometric Temperature Sensors

ACS Appl Mater Interfaces. 2023 Aug 9;15(31):37696-37705. doi: 10.1021/acsami.3c07544. Epub 2023 Jul 27.

Authors

Laurens Bourda^{1

2}, Anna M Kaczmarek³, Min Peng¹, Sonali Mohanty³, Hannes Rijckaert⁴, Pascal Van Der Voort², Kristof Van Hecke¹

Affiliations

¹ XStruct, Department of Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium.
² Center for Ordered Materials, Organometallics and Catalysis (COMOC), Department of Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium.
³ NanoSensing Group, Department of Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium.
⁴ SCRiPTS, Department of Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium.

PMID: 37498184
DOI: 10.1021/acsami.3c07544

Abstract

In this study, we report hybrid crystalline lanthanide-containing 3D covalent organic framework (Ln@3D COF) materials that are suitable for temperature sensing applications. Different routes to obtain these hybrid materials were tested and compared for material quality and thermometric properties. In the first approach, a bipyridine-containing 3D COF (Bipy COF) was grafted with a range of visible emitting lanthanide (Eu³⁺, Tb³⁺, Dy³⁺, and Eu³⁺/Tb³⁺) β-diketonate complexes. In the second approach, a novel nanocomposite material was prepared by embedding NaYF₄:Er,Yb nanoparticles on the surface of a nonfunctionalized 3D COF (COF-300). To the best of our knowledge, the luminescent materials developed here are the first 3D COFs to be tested as ratiometric temperature sensors. In fact, for the Bipy COF, two different types of thermometers were tested (the Eu³⁺/Tb³⁺ system and a rare Dy³⁺ system), with both showing excellent temperature sensing properties. The reported NaYF₄:Er,Yb/COF-300 nanocomposite material combines upconverting nanoparticles with 3D COFs, similar to previously reported metal organic framework (MOF) nanocomposite materials; however, this type of hybrid material has not yet been explored for COFs. As such, our findings open a new pathway toward potential multifunctional materials that can combine thermometry with other modalities, such as catalysis or drug delivery, in just one nanocomposite material.

Keywords: Covalent Organic Frameworks; Lanthanides; Post-Modification; Ratiometric Thermometers; Upconverting Nanoparticles.