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Group 14 Metallafluorenes as Sensitive Luminescent Probes of Surfactants in Aqueous Solution

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Abstract

Sila- and germafluorenes containing alkynyl(aryl) substituents at the 2,7- position are strongly emissive with high quantum yields in organic solvents. Provided they are sufficiently soluble in water, their hydrophobic structures have the potential for many biological and industrial applications in the detection and characterization of lipophilic structures. To that end, the emission behaviors of previously synthesized 2,7- bis[alkynyl(biphenyl)]-9,9-diphenylsilafluorene (1), 2,7- bis[alkynyl(methoxynaphthyl)]-9,9-diphenylgermafluorene (2), 2,7- bis[alkynyl(p-tolyl)]-9,9-diphenylsilafluorene (3), and 2,7- bis[alkynyl(m-fluorophenyl)]-9,9-diphenylsilafluorene (4) were characterized in aqueous solution and in the presence of various surfactants. Despite a high degree of hydrophobicity, all of these metallafluorenes (MFs) are soluble in aqueous solution at low micromolar concentrations and luminesce in a common aqueous buffer. Further, the 2,7 substituent makes the emission behavior tunable (up to 30 nm). Fold emission enhancements in the presence of various surfactants are highest toward Triton X-100 and CTAB (ranging from 5 to 25 fold) and are lowest for the anionic surfactants SDS and SDBS. These enhancements are competitive with existing probes of surfactants. Quantum yields in buffer range from 0.11 to 0.34, competitive with many common fluorophores in biological use. Strikingly, MF quantum yields in the presence of TX-100 and CTAB approach 100 % quantum efficiency. MF anisotropies are dramatically increased only in the presence of TX-100, CTAB, and CHAPS. Coupled with the above data, this suggests that MFs associate with neutral and charged surfactant aggregates. Interactions with the anionic surfactants are weaker and/or leave MFs solvent exposed. These properties make metallafluorenes competitive probes for surfactants and their properties and behaviors, and thus could also have important biological applications.

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Data Availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

Abbreviations

CHAPS:

3-[(3-Cholamidopropyl)dimethylammonio]-1-propanesulfonate

CMC:

critical micelle concentration

CTAB:

cetyltrimethylammonium bromide

SDS:

sodium dodecyl sulfate

SDBS:

Sodium dodecylbenzenesulfonate

MF:

metallafluorene

TX:

Triton X-100

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Funding

This work was supported by the National Science Foundation (to Janet Braddock-Wilking) CHE-1362431.

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Authors and Affiliations

  1. Department of Chemistry & Biochemistry, University of Missouri St. Louis, St. Louis, MO, 63121, USA

    Helena J. Spikes, Shelby J. Jarrett-Noland, Stephan M. Germann, Janet Braddock-Wilking & Cynthia M. Dupureur

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  1. Helena J. Spikes
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  2. Shelby J. Jarrett-Noland
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  3. Stephan M. Germann
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  4. Janet Braddock-Wilking
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  5. Cynthia M. Dupureur
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Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Helena Spikes, Shelby Jarrett-Noland and Stephan Germann. The first draft of the manuscript was written by Cynthia Dupureur and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Cynthia M. Dupureur.

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Spikes, H.J., Jarrett-Noland, S.J., Germann, S.M. et al. Group 14 Metallafluorenes as Sensitive Luminescent Probes of Surfactants in Aqueous Solution. J Fluoresc 31, 961–969 (2021). https://doi.org/10.1007/s10895-021-02730-3

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  • DOI: https://doi.org/10.1007/s10895-021-02730-3

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