Difluoroboron β-diketonate (BF 2 bdk) compounds show environment-sensitive optical properties in solution, aggregation-induced emission (AIE) and multi-stimuli responsive fluorescence switching in the solid state. Here, a series of 4-azepane-substituted β-diketone (bdk) ligands ( L-H , L-OMe , L-Br ) and their corresponding difluoroboron dyes ( D-H , D-OMe , D-Br ) were synthesized, and various responsive fluorescence properties of the compounds were studied, including solvatochromism, viscochromism, AIE, mechanochromic luminescence (ML) and halochromism. Compared to the β-diketones, the boron complexes exhibited higher extinction coefficients but lower quantum yields, and red-shifted absorption and emission in CH 2 Cl 2 . Computational studies showed that intramolecular charge transfer (ICT) dominated rather than π–π* transitions in all the compounds regardless of boron coordination. In solution, all the bdk ligands and boron dyes showed red-shifted emission in more polar solvents and increased fluorescence intensity in more viscous media. Upon aggregation, the emission of the β-diketones was quenched, however, the boronated dyes showed increased emission, indicative of AIE. Solid-state emission properties, ML and halochromism, were investigated on spin cast films. For ML, smearing caused a bathochromic emission shift for L-Br , and powder X-ray diffraction (XRD) patterns showed that the “as spun” and thermally annealed states were more crystalline and the smeared state was amorphous. No obvious ML emission shift was observed for L-H or L-OMe , and the boronated dyes were not mechano-active. Trifluoroacetic acid (TFA) and triethylamine (TEA) vapors were used to study halochromism. Large hypsochromic emission shifts were observed for all the compounds after exposure to TFA vapor, and reversible fluorescence switching was achieved using the acid/base pair.
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J-dimer emission in interwoven metal–organic frameworks
J-dimer emission is an emergent property that occurs when pairs of ground state fluorophores associate, typically in a dilute solution medium. The resulting fluorescence is shifted with respect to the monomer. J-dimer emission, however, has never been observed in concentrated dispersions or in the solid state. We posited that multivariate (MTV) MOFs with double interwoven structures would help to isolate these dimers within their crystalline matrix. Using this strategy, J-aggregate density was controlled during crystallization by following a substitutional solid solution approach. Here, we identified the presence of J-dimers over the entire composition range for interwoven PIZOF-2 / NNU-28 structures with variable amounts of a diethynyl-anthracene aggregate-forming link. We produced bulk crystals that systematically shifted their fluorescence from green to red with lifetimes (up to 13 ns) and quantum yields (up to 76%) characteristic of π–π stacked aggregates. Photophysical studies also revealed an equilibrium constant of dimerization, K D = 1.5 ± 0.3 M −1 , enabling the first thermodynamic quantification of link–link interactions that occur during MOF assembly. Our findings elucidate the role that supramolecular effects play during crystallization of MTV MOFs, opening pathways for the preparation of solid-state materials with solution-like properties by design.
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- Award ID(s):
- 1665277
- NSF-PAR ID:
- 10197388
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 11
- Issue:
- 17
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 4391 to 4396
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0sc00876a
