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Long-Range LMCT Coupling in EuIII Coordination Polymers for an Effective Molecular Luminescent Thermometer*.

Chemistry (Weinheim an der Bergstrasse, Germany) (2020-07-04)
Yuichi Kitagawa, Marina Kumagai, Pedro Paulo Ferreira da Rosa, Koji Fushimi, Yasuchika Hasegawa
ABSTRACT

A design for an effective molecular luminescent thermometer based on long-range electronic coupling in lanthanide coordination polymers is proposed. The coordination polymers are composed of lanthanide ions EuIII and GdIII , three anionic ligands (hexafluoroacetylacetonate), and a chrysene-based phosphine oxide bridges (6,12-bis(diphenylphosphoryl)chrysene). The zig-zag orientation of the single polymer chains induces the formation of packed coordination structures containing multiple sites for CH-F intermolecular interactions, resulting in thermal stability above 350 °C. The electronic coupling is controlled by changing the concentration of the GdIII ion in the EuIII -GdIII polymer. The emission quantum yield and the maximum relative temperature sensitivity (Sm ) of emission lifetimes for the EuIII -GdIII polymer (Eu:Gd=1:1, Φtot =52 %, Sm =3.73 % K-1 ) were higher than those for the pure EuIII coordination polymer (Φtot =36 %, Sm =2.70 % K-1 ), respectively. Enhanced temperature sensing properties are caused by control of long-range electronic coupling based on phosphine oxide with chrysene framework.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Diphenylphosphine, 98%
Sigma-Aldrich
Gadolinium(III) acetate hydrate, 99.9% trace metals basis