Edge Article
Chemical Science
independent from the sequence of metal addition. In addition,
featuring catalytic and luminescent centers, the SCNPs were
employed as a homogeneous catalytic system. The selective
coordination of two metal species exhibiting different func-
tionalities represents, to this date, an unprecedented concept in
the realm of single-chain nanoparticles. The combinatorial
design of catalytically active and luminescent properties within
a SCNP system may not only allow the visualization of the
catalyst (and its separation), yet tracking for specic systems
seems practicable.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
C. B.-K. and P. W. R. acknowledge support from the SFB 1176
(project A2) funded by the German Research Council (DFG). H.
R.'s and N. K.'s PhD studies were additionally supported by the
Fonds der Chemischen Industrie (FCI). C. B. -K. acknowledges
key support from the Australian Research Council (ARC) in the
context of a Laureate Fellowship enabling his photochemical
research program as well as by the Queensland University of
Technology (QUT) for continued support via its Centre for
Materials Science. C. B. -K. additionally acknowledges
continued support by the Helmholtz association via the STN
and BIFTM programs. C. Zovko is thanked for her help
regarding the PL measurements and E. Rosas Valdez is
acknowledged for the synthesis of [Eu(tta)3(H2O)2].
Fig. 5 (Top): Reaction of aniline with allyl alcohol catalyzed by Eu(III)/
Pt(II)–SCNPs. (Bottom): Exemplary separation of the Eu(tta)(III)/Pt(II)–
SCNPs via a short column chromatography (neutral aluminium oxide;
acetone) subsequent to the catalytic reaction. Photographs were
taken upon illumination with an UV-lamp (lexc. ¼ 365 nm). Picture 2
marks the addition of the reaction mixture to the column.
chromatography (e.g. acetone, neural aluminum oxide). In the
latter case, they remained on top of the column and were readily
detected when irradiated with UV light (Fig. 5, applying
Eu(tta)(III)/Pt(II)–SCNPs as catalyst). Thus, for this specic reac-
tion a simple detection mode for the catalyst's separation was
achieved. UV illumination of the ltrate aer column chroma-
tography showed no luminescence, thus indicating a complete
catalyst separation. However, the photoluminescence of the
catalyst is visibly reduced during catalysis, most likely due to the
formation of H2O and thermal decomposition, leading to
partial quenching of the Eu(III) species over time (ESI, Fig. S33†).
Thus, recycling of the catalyst, as it has been previously studied
for Pt(II)–SCNPs,8 was not further pursued, as the luminescence
was signicantly reduced in the second cycle. Additionally, in
case of the Eu(tta)(III)/Pt(II)–SCNPs 19F NMR studies revealed that
the diketonate ligands of the Eu(III) complex are partially
removed with increasing reaction temperature and time. Addi-
tionally, in the eluant of the chromatography a weak resonance
in the 19F NMR spectrum is detected, attributed to unbound tta
ligands, conrming partial decomposition during catalysis.
Advantageously, the amount of phosphine and phosphine
oxide moieties can readily be adjusted. Thus, for future studies,
an introduction of task-specic quantities of Pt(II) and Eu(III)
centers, as well as the implementation of other metal combi-
nations, is feasible.
Notes and references
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Conclusions
In summary, a bifunctional terpolymer containing two orthog-
onal ligand moieties was synthesized via NMP, giving way to the 10 T. Terashima, T. Mes, T. F. A. De Greef, M. A. J. Gillissen,
facile formation of heterometallic Eu(III)/Pt(II)–SCNPs. The
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