π‐Conjugated Donor and Donor–Acceptor Metallo‐Polymers

Wild, Andreas; Schlütter, Florian; Pavlov, G. G.; Friebe, Christian; Festag, Grit; Winter, Andreas; Hager, Martin D.; Cimrová, Věra; Schubert, Ulrich S.

doi:10.1002/marc.200900889

Cited by 40 publications

(37 citation statements)

References 35 publications

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“…Hydrodynamic and atomic force microscopy experiments on related bis-terpyridine coordination polymers, containing transition metals like Ni 2+ , Fe 2+ , Ru 2+ or Zn 2+ , identified a linear conformation for all of these polymers. 4,16,25,47,48 Thus, these experiments are in agreement with the herein presented results and further corroborate the linear rod-like structure of the investigated Zn 2+ -bis-terpyridine coordination polymer. Fig.…”

Section: Excitation-polarization Modulationsupporting

confidence: 94%

Fluorescence quenching in Zn2+-bis-terpyridine coordination polymers: a single molecule study

et al. 2012

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A Zn 2+ -bis-terpyridine coordination polymer is investigated by single-molecule fluorescence spectroscopy (SMS). The bis-terpyridine ligands of the coordination polymers bear conjugated chromophores connecting the terpyridine spheres of the ligands, which resemble structural features of MEH-PPV. To the best of our knowledge this paper presents the first systematic SMS study on Zn 2+ -bis-terpyridine coordination polymers. Upon incorporation of free chromophores into the polymer, the fluorescence quantum yield of individual chromophores appears to be reduced. The reason for the reduced emission per chromophore in a polymer is investigated by brightness studies on single isolated polymer molecules. Furthermore, the experiments reveal that the Zn 2+ -bis-terpyridine coordination polymer contains a significantly larger fraction of effective chromophores, compared to one of the most common conjugated polymers, e.g., MEH-PPV. This finding is attributed to the particularly rigid geometry of the system at hand, which was corroborated by polarization-dependent experiments. Time-resolved experiments identified two different types of intensity fluctuations: small amplitude intensity fluctuations might correlate with switching of individual chromophores by structural fluctuations, while large amplitude jumps switch off the emission of the entire molecule. Finally, experiments under different atmospheric conditions offer further insights into the molecular mechanism and the nature of the quenchers involved in the blinking.

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Section: Excitation-polarization Modulationsupporting

confidence: 94%

Fluorescence quenching in Zn2+-bis-terpyridine coordination polymers: a single molecule study

et al. 2012

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“…Moreover, the corresponding metal complexes may be used for the construction of OLEDs and solar cells (for the first results of a study in this direction see, for example, ref. [49] ).…”

Section: Discussionmentioning

confidence: 93%

π‐Conjugated 2,2′:6′,2″‐Bis(terpyridines): Systematical Tuning of the Optical Properties by Variation of the Linkage between the Terpyridines and the π‐Conjugated System

et al. 2010

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Abstract2,2′:6′,2″‐Terpyridines bearing well‐defined π‐conjugated substituents at the 4′‐position are known to exhibit interesting electronic and optical properties. The systematic variation of both the spacer unit and the linker in conjugated bis(terpyridines) has resulted in a library of π‐conjugated systems, enabling the study of the structure–property relationships of these materials. We have proven the Huisgen 1,3‐dipolar cycloaddition reaction to be a versatile tool for connecting conjugated systems, even though the conjugation is hindered by the introduced triazole moiety. All the terpyridine derivatives were fully characterized by 1H and 13C NMR spectroscopy, UV/Vis absorption and emission measurements as well as MALDI‐TOF MS. Thin films of the materials were produced by spin‐coating and subsequently characterized. Because tuning of the band gap of the materials over a wide range is possible, quantum yields of up to 85 % and extinction coefficients of around 100000 M–1 cm–1 could be observed, the compounds might be promising candidates for the design of new functional supramolecular materials.

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“…Among them, ligands of the tpy-ethynyl type have proven to be very useful and provide a library of photoresponsive complexes derived from the basic Ru(II)-tpy type module [23–27]. Recently, tpy-complexes that incorporate π-conjugated thiophene or thienylene-ethynylene units became available, and the study of their photophysical properties is of great relevance, given the importance of oligothiophene and tpy-units as electro- and photoactive conjugated materials [21,28–32].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru(II) complexes

Mishra¹,

Mena‐Osteritz²,

Bäuerle³

2013

Beilstein J. Org. Chem.

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SummaryPd-catalyzed Sonogashira cross-coupling reactions were used to synthesize novel π-conjugated oligothienylene-ethynylene dendrons and their corresponding terpyridine-based ligands. Their complexation with Ru(II) led to interesting novel metallodendrimers with rich spectroscopic properties. All new compounds were fully characterized by 1H and 13C NMR, as well as MALDI–TOF mass spectra. Density functional theory (DFT) calculations performed on these complexes gave more insight into the molecular orbital distributions. Photophysical and electrochemical studies were carried out in order to elucidate structure–property relationships and the effect of the dendritic structure on the metal complexes. Photophysical studies of the complexes revealed broad absorption spectra covering from 250 to 600 nm and high molar extinction coefficients. The MLCT emission of these complexes were significantly red-shifted (up to 115 nm) compared to the parent [Ru(tpy)2]2+ complex.

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π‐Conjugated Donor and Donor–Acceptor Metallo‐Polymers

Cited by 40 publications

References 35 publications

Fluorescence quenching in Zn2+-bis-terpyridine coordination polymers: a single molecule study

Fluorescence quenching in Zn2+-bis-terpyridine coordination polymers: a single molecule study

π‐Conjugated 2,2′:6′,2″‐Bis(terpyridines): Systematical Tuning of the Optical Properties by Variation of the Linkage between the Terpyridines and the π‐Conjugated System

Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru(II) complexes

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