An Amphiphilic Pentaaryl Cyclopentadienyl Ruthenium(II) Molecular Rotor with a Luminescent Tag

Toshio Nishino; Yorie Ohno; Mika Ishihara; Yoshiko Nishikawa; Colin J. Martin; Kazuma Yasuhara; Gwénaël Rapenne

doi:10.1055/a-2503-7748

Synlett, Table of Contents

Synlett 2025; 36(09): 1237-1241
DOI: 10.1055/a-2503-7748

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Supramolecular Catalysis and Molecular Switches

An Amphiphilic Pentaaryl Cyclopentadienyl Ruthenium(II) Molecular Rotor with a Luminescent Tag

Toshio Nishino

^aDivision of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

,

Yorie Ohno

^aDivision of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

,

Mika Ishihara

^aDivision of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

,

Yoshiko Nishikawa

^aDivision of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

,

Colin J. Martin

^aDivision of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

,

Kazuma Yasuhara

^aDivision of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

^bCenter for Digital Green-Innovation, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

^cMedilux Research Center, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

,

Gwénaël Rapenne ∗

^aDivision of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama, Ikoma, 630-0192, Japan

^dCEMES, Université de Toulouse, CNRS, 29, rue Marvig, 31055 Toulouse, France

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Abstract

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Abstract

This study presents a chemically modified molecular motor designed for interactions with lipid bilayers. By incorporating long alkyl chains into the anchoring fragment and a rhodamine luminescent tag onto the rotating subunit, we aimed to monitor the position of the motor and to permit its real-time visualization during membrane-perforation experiments. The synthesis of the functionalized tripodal ligand involved a seven-step process, culminating in the formation of a piano-stool Ru(II) complex that exhibits distinctive spectroscopic properties. The luminescence of the rhodamine tag, although slightly quenched upon incorporation in the Ru(II) complex, remains sufficiently strong to permit single-molecule observation using a total-internal-reflection fluorescence microscope.

Key words

molecular rotors - ruthenium complexes - fluorescent tags - amphiphiles - membrane penetration

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References

References and Notes
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19 Fluorescence-Tagged Molecular Rotor 10 For other compounds, refer to the Supporting Information. A mixture of compound 9 (295 mg, 160 μmol), alkyne-substituted rhodamine derivative 11 ⁴ (102 mg, 195 μmol), CuI (19 mg, 100 μmol), and TBTA (44 mg, 82 μmol) was suspended in anhyd THF (17 mL), and the resulting mixture was refluxed for 18 h. After removal of volatiles, the crude compound was purified by column chromatography [silica gel, CHCl₃–MeOH (10:1)] to give a brown solid; yield: 71% (270 mg). ¹H NMR (400 MHz, CDCl₃/TMS): δ = 8.38 (br s, 1 H, NH), 8.11 (d, J = 0.8 Hz, 1 H, H_d), 7.93 (s, 3 H, H_d), 7.89 (s, 3 H, H_a), 7.63 (br s, 1 H), 7.56–7.53 (m, 5 H, H_Ar), 7.44–7.42 (m, 2 H, H_Ar), 7.38–7.31 (m, 14 H, H_Ar), 7.28–7.26 (m, 12 H, H_Ar with CHCl₃), 7.11–7.06 (m, 4 H, H_Ar), 7.00–6.96 (m, 12 H, H_Ar), 6.55 (d, J = 9.2 Hz, 2 H, H_xanthene), 6.44 (d, J = 2.0 Hz, 2 H, H_xanthene), 6.33 (d, J = 8.0 Hz, 2 H, H_xanthene), 5.55 (s, 4 H, H_a-b), 4.75 (s, 2 H, H_e), 3.89 (s, 6 H, H_e), 3.35 [q, J = 6.9 Hz, 8 H, NEt (CH₂)], 2.49 (t, J = 7.2 Hz, 6 H, H_f), 1.66–1.58 (m, 14 H, alkyl chains including H₂O), 1.39–1.25 (m, 54 H, CH_{2 Alkyl}), 1.16 [t, J = 7.2 Hz, 12 H, NEt (CH₃)], 0.87 (t, J = 6.8 Hz, 9 H, CH₃). ¹³C NMR (150 MHz, CDCl₃/TMS): δ = 166.2, 153.8, 148.0, 143.6, 140.7, 140.3, 136.8, 134.2, 133.9, 133.9, 133.8, 133.6, 129.2, 128.9, 128.7, 128.5, 127.8, 127.2, 127.1, 124.4, 122.1, 121.9, 120.0, 119.5, 111.3, 108.6, 97.4, 88.2, 88.0, 87.2, 53.8, 44.6, 37.3, 31.9, 29.7, 29.7, 29.6, 29.4, 29.2, 29.0, 22.7, 14.1, 12.5. HRMS (ESI, positive): m/z [M + H]⁺ calcd for C₁₄₃H₁₆₅BN₁₅O₄RuS₃: 2365.1468; found: 2365.1184. UV/Vis (CHCl₃, 10 μM): λ_max (ε) = 550 nm (16270). Emission (λ_exc = 520 nm; CHCl₃, 10 μM): λ_max : 569 nm.

Supplementary Material

Supporting Information