Intense Dyes through Chromophore-Chromophore Interactions: Bi- and Trichromophoric Perylene-3,4:9,10-bis(dicarboximide)s

Langhals, Heinz; Jona, Wolfgang

doi:10.1002/(sici)1521-3773(19980420)37:7<952::aid-anie952>3.0.co;2-4

Cited by 96 publications

(58 citation statements)

References 5 publications

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“…[2][3][4][5] The mobility of singlet excitons is derived mainly from the Coulombic coupling between chromophores, consistent with the fundamental excitations being Frenkel-type excitons where the electron and hole remain bound to the parent molecule. However, in tightlypacked π-stacked organic crystals, such as those corresponding to a multitude of perylene-based dyes [6][7][8] , the close proximity of neighboring molecules leads to significant charge transfer (CT) between chromophores through the spatial overlap of their frontier molecular orbitals. It is well known that the electron and hole bandwidths, as well as the optical bandgap in perylene dyes, are very sensitive to sub-Å shifts ("slips") in the relative orientations of neighboring molecules, leading to the remarkable range of colors displayed by such dyes in the crystalline phase.…”

Section: Introductionmentioning

confidence: 99%

Exciton mobility control throughsub−Åpacking modifications in molecular crystals

et al. 2015

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Exciton mobility in π-stacks of organic chromophores is shown to be highly sensitive to the interference between long-range Coulomb coupling and a short-range coupling due to wave function overlap. A destructive interference which leads to a compromised exciton bandwidth can be converted to constructive interference (and an enhanced bandwidth) upon sub-Å transverse displacements between neighboring chromophores. The feasibility of the control scheme is demonstrated theoretically on a derivative of terrylene, where the exciton is essentially immobile despite strong Coulombic coupling. A transverse slip of only 0.5 Å along either the short or long molecular axis boosts the exciton velocity to 4 2 10 × m/sec. Changes in the mobility are correlated to changes in the absorption spectrum, allowing the latter to be used as a screen for high-mobility aggregates.

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Section: Introductionmentioning

confidence: 99%

Exciton mobility control throughsub−Åpacking modifications in molecular crystals

et al. 2015

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“…[1][2][3][4] Perylene diimides (PDIs) derivatives effectively form supramolecular assemblies through p-p stacking interaction. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] In particular, supramolecular assemblies based on calixarenePDI conjugates show efficient energy and electron transfer properties due to the well-defined rigid and electron-rich scaffolds of calixarenes. [22][23][24][25][26][27] We have prepared PDI derivatives with a high emission property in aqueous solutions.…”

Section: Introductionmentioning

confidence: 99%

Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

Takashima

Otsubo

et al. 2012

Polym J

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Perylene diimide (PDI) derivatives with cyclodextrins (PDI-CD 2 s) exhibit specific emission properties, which depend on the type of CDs in an aqueous solution. Herein we successfully create an emission film-kneaded PDI-CD 2 derivatives via effective tumbling of the altropyranose unit. PDI-6CD 2 s are crosslinked with PDI between 6-amino-CDs. Although the emission intensities of PDI-6CD 2 s in dimethyl sulfoxide are similar regardless of the type of CD, PDI-6cCD 2 has a relatively high emission intensity in aqueous solutions. In contrast, for PDIC 7 -3CD 2 s, which are linked with N,N'-bis(6-carboxylhexyl)perylene-3,4,9,10-tetracarboxyl diimide (BisC 7 -PDI) between 3-amino-CDs, the emission intensity of PDIC 7 -3bCD 2 is stronger than those of PDIC 7 -3aCD 2 , PDIC 7 -3cCD 2 , and PDI-6CD 2 s in aqueous solutions. The selective emission behavior of PDIC 7 -3CD 2 s is due to the formation of the pseudo[1]rotaxane dimer through tumbling of the altropyranose unit in an aqueous solution. PDIC 7 -3bCD 2 in the solid state does not demonstrate a distinctive emission due to self-quenching, whereas PDIC 7 -3bCD 2 kneaded into the polyvinyl alcohol (PVA) film exhibits a bright yellow emission. The order of the emission intensities of PDIC 7 -3CD 2 s kneaded into PVA films is similar to those in aqueous solutions. INTRODUCTIONRecently, supramolecular assemblies with extended aromatic compounds have attracted much attention. 1-4 Perylene diimides (PDIs) derivatives effectively form supramolecular assemblies through p-p stacking interaction. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] In particular, supramolecular assemblies based on calixarenePDI conjugates show efficient energy and electron transfer properties due to the well-defined rigid and electron-rich scaffolds of calixarenes. [22][23][24][25][26][27] We have prepared PDI derivatives with a high emission property in aqueous solutions.Generally, PDI derivatives have low solubilities in aqueous solutions. Even if PDI derivatives are dissolved in aqueous solutions by introducing a hydrophilic group, the emission of PDI derivatives exhibit self-quenching in aqueous solutions due to the formation of supramolecular assemblies and folders. To create water-soluble and effective emission sensor materials with PDI derivatives, we have introduced CDs into the PDI motif. The CDs are a family of macrocyclic oligosaccharides; the most common are composed of 6 (a), 7 (b), or 8 (g) a-1,4-linked D-glucopyranose units. [28][29][30][31][32][33][34] The introduction of CDs should influence the molecular recognition property and increase the emission intensity. Although supramolecular assemblies based on permethylated CDPDI conjugates have been previously reported, 35-38 the formation of assemblies cannot prevent the decrease in the monomer emission intensity of the PDI units due

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“…Special optic effects [9] are expected as a consequence of the interaction of chromophores [24] in the dyads (bichromophores). However, the UV/Vis spectra of the open-chain dyad 5 are nearly identic with the spectra of 1 (Figure 4, left spectrum, red and green curves).…”

Section: Resultsmentioning

confidence: 99%

A Sustainable Preparation of Functional Perylenophanes by Domino Metathesis

Langhals¹,

Rauscher²,

Mayer³

2019

GSC

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A sustainable four-step synthesis of soluble perylenophanes for applications as fluorescent optical functional materials is presented and even allows upscaling because of starting with technical bulk products. Thus, terminal alkenylnitriles were alkylated reduced to amines, condensed with perylenetetracarboxylic bisanhydride and cyclised to cyclophanes by means of double cross metathesis in yields until 69% of isolated dyes. The first metathesis by means of the second-generation Hoveyda-Grubbs-catalyst brings the remaining reactive olefinic groups close together favouring the ring-closure to the cyclophanes where the locked neighboring of chromophores in a skew arrangement induce strong exciton interactions. The latter cause an increased the Stokes' separation by means of a moderate hypsochromic shift of light absorption and a stronger bathochromic shift of fluorescence. Various applications such as for lasers, photonics, solar collectors or in analytics are discussed.

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Intense Dyes through Chromophore-Chromophore Interactions: Bi- and Trichromophoric Perylene-3,4:9,10-bis(dicarboximide)s

Cited by 96 publications

References 5 publications

Exciton mobility control throughsub−Åpacking modifications in molecular crystals

Exciton mobility control throughsub−Åpacking modifications in molecular crystals

Emission properties of cyclodextrin dimers linked with perylene diimide—effect of cyclodextrin tumbling

A Sustainable Preparation of Functional Perylenophanes by Domino Metathesis

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