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Exploring Coumarin-Based Boron Emissive Complexes as Temperature Thermometers in Polymer-Supported Materials.

ABSTRACT: Three coumarin-based boron complexes (L1, L2 and L3) were designed and successfully incorporated into polymeric matrixes for evaluation as temperature probes. The photophysical properties of the complexes were carried out in different solvents and in the solid state. In solution, compound L1 exhibited the highest fluorescence quantum yield, 33%, with a positive solvatochromism also being observed on the absorption and emission when the polarity of the solvent increased. Additionally in the presence of anions, L1 showed a colour change from yellow to pink, followed by a quenching in the emission intensity, which is due to deprotonation with the formation of a quinone base. Absorption and fluorescence spectra of L1 were calculated at different temperatures by the DFT/B3LYP method. The decrease in fluorescence of compound L1 with an increase in temperature seems to be due to the presence of pronounced torsional vibrations of the donor and acceptor fragments relative to the single bond with C(carbonyl)-C (styrene fragment). L1, L2 and L3, through their incorporation into the polymeric matrixes, became highly emissive by aggregation. These dye@doped polymers were evaluated as temperature sensors, showing an excellent fluorescent response and reversibility after 15 cycles of heating and cooling.

SUBMITTER: Pedro G

PROVIDER: S-EPMC9921380 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

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Exploring Coumarin-Based Boron Emissive Complexes as Temperature Thermometers in Polymer-Supported Materials.

Pedro Gonçalo G Duarte Frederico F Cheptsov Dmitrii A DA Volodin Nikita Yu NY Ivanov Ivan V IV Santos Hugo M HM Capelo-Martinez Jose Luis JL Cuerva Cristián C Oliveira Elisabete E Traven Valerii F VF Lodeiro Carlos C

Sensors (Basel, Switzerland) 20230203 3

Three coumarin-based boron complexes (L1, L2 and L3) were designed and successfully incorporated into polymeric matrixes for evaluation as temperature probes. The photophysical properties of the complexes were carried out in different solvents and in the solid state. In solution, compound L1 exhibited the highest fluorescence quantum yield, 33%, with a positive solvatochromism also being observed on the absorption and emission when the polarity of the solvent increased. Additionally in the prese ...[more]

PMID: 36772728

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Project description:Multifunctional optical materials can be realized by combining stimuli-responsive photoluminescence (PL), e.g., optical thermometry, with non-linear optical (NLO) effects, such as second-harmonic generation (SHG). We report a novel approach towards SHG-active luminescent thermometers achieved by constructing unique iridium(iii) complexes, cis-[IrIII(CN)2(R,R-pinppy)2]- (R,R-pinppy = (R,R)-2-phenyl-4,5-pinenopyridine), bearing both a chiral 2-phenylpyridine derivative and cyanido ligands, the latter enabling the formation of a series of molecular materials: (TBA)[IrIII(CN)2(R,R-pinppy)2]·2MeCN (1) (TBA+ = tetrabutylammonium) and (nBu-DABCO)2[IrIII(CN)2(R,R-pinppy)2](i)·MeCN (2) (nBu-DABCO+ = 1-(n-butyl)-1,4-diazabicyclo-[2.2.2]octan-1-ium) hybrid salts, (TBA)2{[LaIII(NO3)3(H2O)0.5]2[IrIII(CN)2(R,R-pinppy)2]2} (3) square molecules, and {[LaIII(NO3)2(dmf)3][IrIII(CN)2(R,R-pinppy)2]}·MeCN (4) coordination chains. Thanks to the chiral pinene group, 1-4 crystallize in non-centrosymmetric space groups leading to SHG activity, while the N,C-coordination of ppy-type ligands to Ir(iii) centers generates visible charge-transfer (CT) photoluminescence. The PL characteristics are distinctly temperature-dependent which was utilized in achieving ratiometric optical thermometry below 220 K. The PL phenomena were rationalized by DFT/TD-DFT calculations indicating an MLCT-type of the emission in obtained Ir(iii) complexes with the rich vibronic structure providing a few emission bands that variously depend on temperature due to the role of thermally activated vibrations. As these crucial vibrational modes depend on the crystal lattice, the thermometry performance differs within 1-4 being the most efficient in 4 while the SHG is by far the best also for 4. This proves that pinene-functionalized cyclometalated dicyanidoiridates(iii) are great prerequisites for tunable PL-NLO conjunction with the most effective multifunctionality ensured by the insertion of these anions into bimetallic frameworks.

Dataset Information

Exploring Coumarin-Based Boron Emissive Complexes as Temperature Thermometers in Polymer-Supported Materials.

Publications

Exploring Coumarin-Based Boron Emissive Complexes as Temperature Thermometers in Polymer-Supported Materials.

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