Polymer Glass Transitions Switch Electron Transfer in Individual Molecules

Siekierzycka, Joanna R.; Hippius, Catharina; Würthner, Frank; Williams, René M.; Brouwer, Albert M.

doi:10.1021/ja905667c

Cited by 46 publications

(35 citation statements)

References 18 publications

(25 reference statements)

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“…[250] From these studies a wealth of information could be derived for many photophysical processes such as energy transfer or annihilation phenomena, [205] as well as morphological transitions in polymeric matrices. [251] These covalent multichromophore ensembles will, however, not be discussed here as we put our focus on self-assembled H-and J-aggregates of PBIs as illustrative examples for dye-aggregate-based exciton transport systems. Towards such aggregate systems PBIs bear another advantage: These dyes are among the most strongly aggregating dye molecules known, showing sufficiently high binding constants not only in water [252] (where solvophobic effects prevail), but also in aliphatic and even in aromatic solvents.…”

Section: Supramolecular Systems: Perylene Bisimide H-and J-aggregatesmentioning

confidence: 99%

Exciton Transport in Molecular Aggregates – From Natural Antennas to Synthetic Chromophore Systems

Brixner

Hildner

Köhler

et al. 2017

Advanced Energy Materials

291

301

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The transport of excitation energy in molecular aggregates is of crucial importance for the function of organic optoelectronic devices and next‐generation solar cells. First, this review summarizes the theoretical background of the nature of the electronically excited states of molecular aggregates. For these systems, the electronic interaction between the monomers leads to the formation of exciton states. This goes along with a shift of the excitation energies and a redistribution of the oscillator strength with respect to the monomers. Next, a brief overview is provided over experimental techniques that allow to study the properties of excitons in molecular aggregates. This includes single‐molecule spectroscopy, coherent two‐dimensional (2D) spectroscopy, and single‐molecule coherent spectroscopy. Finally, examples of molecular aggregates spanning the range from natural systems that act in photosynthesis as light‐harvesting antennas to artificial aggregates built from synthetic chromophores are illustrated.

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Section: Supramolecular Systems: Perylene Bisimide H-and J-aggregatesmentioning

confidence: 99%

Exciton Transport in Molecular Aggregates – From Natural Antennas to Synthetic Chromophore Systems

Brixner

Hildner

Köhler

et al. 2017

Advanced Energy Materials

291

301

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“…This points towards a heterogeneous distribution of free volume, as previously discussed for single-molecule rotation measurements [31] as well as for polymers with different T g values through single-molecule photoinduced electron-transfer studies. [32,33] Besides the photoswitching kinetics, the photostability of the probes determines their suitability for super-resolution fluorescence microscopy techniques. As shown in Figure 3, our photoswitch can perform many on-off cycles before photobleaching.…”

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confidence: 99%

Nanoscopic Visualization of Soft Matter Using Fluorescent Diarylethene Photoswitches

et al. 2016

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The in situ imaging of soft matter is of paramount importance for a detailed understanding of functionality on the nanoscopic scale. Although super-resolution fluorescence microscopy methods with their unprecedented imaging capabilities have revolutionized research in the life sciences, this potential has been far less exploited in materials science. One of the main obstacles for a more universal application of superresolved fluorescence microscopy methods is the limitation of readily available suitable dyes to overcome the diffraction limit. Here, we report a novel diarylethene-based photoswitch with a highly fluorescent closed and a nonfluorescent open form. Its photophysical properties, switching behavior, and high photostability make the dye an ideal candidate for photoactivation localization microscopy (PALM). It is capable of resolving apolar structures with an accuracy far beyond the diffraction limit of optical light in cylindrical micelles formed by amphiphilic block copolymers.The nanoscopic structure of soft-matter materials determines their properties. [1] Therefore, methods to directly visualize structures in the nanometer range are of paramount importance for the ongoing evolution of novel materials with specialized and adaptive properties for sophisticated applications. Scanning probe microscopy techniques give access to the nanometer range and determine surface properties such as topology and softness, [2,3] while modern electron microscopy methods, such as scanning electron microscopy (SEM) [4,5] and transmission electron microscopy (TEM), [6][7][8] can yield structural information even in the subnanometer range when there is sufficient electron density contrast. Despite the success of these methods, they are technically demanding and time-consuming. Furthermore, many softmatter samples possess poor electron contrast, and require non-invasive in situ imaging below the surface as well as the possibility to directly study dynamics. In recent years, superresolved fluorescence microscopy has revolutionized optical imaging, [9][10][11][12][13][14] by utilizing the photophysical or photochemical switching of fluorescent dyes in a sophisticated manner in combination with modern optics. So far, the life sciences have benefited, in particular, from the new possibilities of resolving structures well beyond the diffraction limit of light. Only a few examples of the application of super-resolution microscopy to materials science have been reported, [15][16][17][18] since concepts that require, for example, the addition of (polar) switching buffers often fail for these systems. Therefore, the main bottleneck for more universal applications of super-resolution imaging are switchable dyes with suitable (photo-)physical and chemical properties, such as high photostability, adjustable switching rates, minimum interaction with the environment to be probed, and simple design, with the possibility of multiple and straightforward derivatization for the specific labeling of structures or compartments. [19] ...

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“…[1] With this unique combination of optical and electronic properties they have entered many research fields, including organic electronics, [2] optical sensing, [3] single-molecule spectroscopy [4] and supramolecular photochemistry. [1] With this unique combination of optical and electronic properties they have entered many research fields, including organic electronics, [2] optical sensing, [3] single-molecule spectroscopy [4] and supramolecular photochemistry.…”

mentioning

confidence: 99%

Near‐IR Phosphorescent Ruthenium(II) and Iridium(III) Perylene Bisimide Metal Complexes

2014

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The phosphorescence emission of perylene bisimide derivatives has been rarely reported. Two novel ruthenium(II) and iridium(III) complexes of an azabenz-annulated perylene bisimide (ab-PBI), [Ru(bpy)2 (ab-PBI)][PF6 ]2 1 and [Cp*Ir(ab-PBI)Cl]PF6 2 are now presented that both show NIR phosphorescence between 750-1000 nm in solution at room temperature. For an NIR emitter, the ruthenium complex 1 displays an unusually high quantum yield (Φp ) of 11 % with a lifetime (τp ) of 4.2 μs, while iridium complex 2 exhibits Φp <1 % and τp =33 μs. 1 and 2 are the first PBI-metal complexes in which the spin-orbit coupling is strong enough to facilitate not only the Sn →Tn intersystem crossing of the PBI dye, but also the radiative T1 →S0 transition, that is, phosphorescence.

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Polymer Glass Transitions Switch Electron Transfer in Individual Molecules

Cited by 46 publications

References 18 publications

Exciton Transport in Molecular Aggregates – From Natural Antennas to Synthetic Chromophore Systems

Exciton Transport in Molecular Aggregates – From Natural Antennas to Synthetic Chromophore Systems

Nanoscopic Visualization of Soft Matter Using Fluorescent Diarylethene Photoswitches

Near‐IR Phosphorescent Ruthenium(II) and Iridium(III) Perylene Bisimide Metal Complexes

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