Meta-Alkoxy-Substituted Difluoroboron Dibenzoylmethane Complexes as Environment-Sensitive Materials

Margaret L. Daly; Caroline Kerr; Christopher A. Derosa; Cassandra L. Fraser

doi:10.1021/acsami.7b06910

Meta-Alkoxy-Substituted Difluoroboron Dibenzoylmethane Complexes as Environment-Sensitive Materials

Margaret L. Daly, Caroline Kerr, Christopher A. Derosa, Cassandra L. Fraser

Research output: Contribution to journal › Article › peer-review

45 Scopus citations

Abstract

The optical properties of meta-alkoxy-substituted difluoroboron dibenzoylmethane dyes were investigated in solution and in the solid state. Meta-alkoxy substitution induced strong intramolecular charge transfer (ICT) from the oxygen-donating substituent to the halide and boron acceptors in the excited state, as compared to the π-π∗ transition that is observed with para-alkoxy substitution. The optical properties of para- and meta-substituted alkoxy boron dyes were evaluated by calculations, in dilute solution, and in solid-state films. When embedded in amorphous matrixes (e.g., PLA, PMMA, PS, cholesterol), all dyes showed fluorescence (F) and phosphorescence (P) emission. In this report, we show that meta-substitution resulted in enhanced solvatochromism and an increased phosphorescence-to-fluorescence ratio in solid-state films compared to analogous para-substituted samples. With enhanced phosphorescence intensity via the heavy-atom effect, iodo-substituted dyes were further studied in PLA-PEG nanoparticles. Oxygen calibrations revealed stronger phosphorescence and a greater oxygen-sensing range for the meta- versus para-alkoxy-substituted dyes, features that are important for oxygen-sensing materials design.

Original language	English (US)
Pages (from-to)	32008-32017
Number of pages	10
Journal	ACS Applied Materials and Interfaces
Volume	9
Issue number	37
DOIs	https://doi.org/10.1021/acsami.7b06910
State	Published - Sep 20 2017
Externally published	Yes

Bibliographical note

Funding Information:
We thank the National Institutes of Health (R01 CA167250) for support of this work. We gratefully acknowledge the UVA Center for Undergraduate Excellence for Harrison Undergraduate Research Awards to M.L.D. and C.K. and the Beckman Scholars Program for a fellowship to C.K. We thank Dr. Tristan Butler and Dr. James N. Demas for helpful discussions.

Publisher Copyright:
© 2017 American Chemical Society.

Keywords

difluoroboron β-diketonate complexes
fluorescence
nanoparticles
oxygen sensing
poly(lactic acid)
room-temperature phosphorescence
solvatochromism

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title = "Meta-Alkoxy-Substituted Difluoroboron Dibenzoylmethane Complexes as Environment-Sensitive Materials",

abstract = "The optical properties of meta-alkoxy-substituted difluoroboron dibenzoylmethane dyes were investigated in solution and in the solid state. Meta-alkoxy substitution induced strong intramolecular charge transfer (ICT) from the oxygen-donating substituent to the halide and boron acceptors in the excited state, as compared to the π-π∗ transition that is observed with para-alkoxy substitution. The optical properties of para- and meta-substituted alkoxy boron dyes were evaluated by calculations, in dilute solution, and in solid-state films. When embedded in amorphous matrixes (e.g., PLA, PMMA, PS, cholesterol), all dyes showed fluorescence (F) and phosphorescence (P) emission. In this report, we show that meta-substitution resulted in enhanced solvatochromism and an increased phosphorescence-to-fluorescence ratio in solid-state films compared to analogous para-substituted samples. With enhanced phosphorescence intensity via the heavy-atom effect, iodo-substituted dyes were further studied in PLA-PEG nanoparticles. Oxygen calibrations revealed stronger phosphorescence and a greater oxygen-sensing range for the meta- versus para-alkoxy-substituted dyes, features that are important for oxygen-sensing materials design.",

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AB - The optical properties of meta-alkoxy-substituted difluoroboron dibenzoylmethane dyes were investigated in solution and in the solid state. Meta-alkoxy substitution induced strong intramolecular charge transfer (ICT) from the oxygen-donating substituent to the halide and boron acceptors in the excited state, as compared to the π-π∗ transition that is observed with para-alkoxy substitution. The optical properties of para- and meta-substituted alkoxy boron dyes were evaluated by calculations, in dilute solution, and in solid-state films. When embedded in amorphous matrixes (e.g., PLA, PMMA, PS, cholesterol), all dyes showed fluorescence (F) and phosphorescence (P) emission. In this report, we show that meta-substitution resulted in enhanced solvatochromism and an increased phosphorescence-to-fluorescence ratio in solid-state films compared to analogous para-substituted samples. With enhanced phosphorescence intensity via the heavy-atom effect, iodo-substituted dyes were further studied in PLA-PEG nanoparticles. Oxygen calibrations revealed stronger phosphorescence and a greater oxygen-sensing range for the meta- versus para-alkoxy-substituted dyes, features that are important for oxygen-sensing materials design.

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Meta-Alkoxy-Substituted Difluoroboron Dibenzoylmethane Complexes as Environment-Sensitive Materials

Abstract

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