Design of Near-Infrared Dyes Based on π-Conjugation System Extension 2. Theoretical Elucidation of Framework Extended Derivatives of Perylene Chromophore

Adachi, and Masafumi; Nagao, Yuki

doi:10.1021/cm000857v

Cited by 70 publications

(65 citation statements)

References 65 publications

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“…The perylene imide dye displays an intense absorption band at around 530 nm, which corresponds to a p!p* transition, the vibronic bands of which are still visible in the spectrum of trimethylsilylacetylene-perylene imide 2. [51,52] Quaterthiophene exhibits a broad p!p* transition at www.chemeurj.org around 400 nm located in the same region as those of the extended TTF. The absorption bands of exTTF are also attributed to p!p* transitions characterized by significant charge transfer from the dithiolium units to the central aromatic core.…”

Section: Resultsmentioning

confidence: 99%

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

Boixel

Blart

Pellegrin

et al. 2010

Chemistry A European J

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Two families of dyad and triad systems based on perylene monoimide (PMI), quaterthiophene (QT), and 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (extended tetrathiafulvalene, exTTF) molecular components have been designed and synthesized. The dyads (D1 and D2) are of the PMI-QT type and the triads (T1 and T2) of the PMI-QT-exTTF type. The two families differ in the saturated or unsaturated nature of the linker groups (ethynylene in D1 and T1, ethylene in D2 and T2) that bridge the molecular components. The dyads and triads have been characterized by electrochemical, photophysical, and computational methods. Both the experimental and the computational (DFT) results indicate that in the unsaturated systems strong intercomponent interactions lead to substantial perturbation of the properties of the subunits. In particular, in T1, delocalization is particularly effective between the QT and exTTF units, which would be better viewed combined as a single electronic subsystem. For the dyad systems, the photophysics observed following excitation of the PMI unit is solvent-dependent. In moderately polar solvents (dichloromethane, diethyl ether) fast charge separation is followed by recombination to the ground state. In toluene, slow conversion to the charge-separated state is followed by intersystem crossing and recombination to yield the triplet state of the PMI unit. The behavior of the triads, on the other hand, is remarkably similar to that of the corresponding dyads, which indicates that, after primary charge separation, hole shift from the oxidized QT component to exTTF is quite inefficient. This unexpected result has been rationalized on the basis of the anomalous (simultaneous two-electron oxidation) electrochemistry of exTTF and with the help of DFT calculations. In fact, although exTTF is electrochemically easier to oxidize than QT by around 0.6 V, the one-electron redox orbitals (HOMOs) of the two units in triad T2 are almost degenerate.

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Section: Resultsmentioning

confidence: 99%

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

Boixel

Blart

Pellegrin

et al. 2010

Chemistry A European J

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“…The chromophoric system of 1 is especially advantageous because the absorption in the VIS is based on only one electronic transition. This was established [27] by measurements of linear dichroism and different quantum-mechanical calculations [83]. The E vector of this transition is located on the connection line of the two imide N-atoms.…”

Section: Furthermentioning

confidence: 88%

Control of the Interactions in Multichromophores: Novel Concepts. Perylene Bis‐imides as Components for Larger Functional Units

Langhals¹

2005

Helvetica Chimica Acta

342

240

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Dedicated to Professor Rolf Huisgen on the occasion of his 85th birthdayThe controlling of the internal interaction in multichromophores leads to functional dyes with novel properties. Such a controlling is demonstrated with perylene dyes and offers a manifold of novel possibilities.1. Introduction. ± Chromophores are responsible for the color of matter and are the basis of well established applications of dyes [1] such as textile dyes, pigments [2], and inks. Whereas the chemistry for such examples is highly developed, chromophores in novel applications are gaining increasing importance; the keywords being functional dyes, these novel applications, in contrast to the well established ones, have recently undergone a very rapid development, the end of which cannot yet be seen. Single chromophores are used in the majority of such novel applications, mostly derived from well investigated basic structures the properties of which were adopted to the requirements of the application. However, such a concept does by far not exhaust the possibilities of chromophores because an even larger range becomes accessible by the interactions in multichromophoric systems. Such a range is not just of interest for novel applications. Nature demonstrates, for example with the photosynthesis reaction center [3 ± 5] and the flower pigments [6 ± 8], how special properties can be obtained by such interactions. However, for this, suitable building blocks are required.

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“…This increase in energy of the HOMOs is attributed to the increasing number of antibonding connections between the naphthalene moieties. [24] The calculated frontier orbitals of coronenebis(dicarbox-A C H T U N G T R E N N U N G imide) show already that CDI cannot be regarded as a simple analogue of rylenebis(dicarboximide)s (Figure 4).…”

Section: Dinaphthoquaterrylenebis(dicarboximide)mentioning

confidence: 97%

Novel Core‐Expanded Rylenebis(Dicarboximide) Dyes Bearing Pentacene Units: Facile Synthesis and Photophysical Properties

Avlasevich

Müller

Erk³

et al. 2007

Chemistry A European J

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Two synthetic routes for the benzannulation in the "bay"-region of rylenebis(dicarboximide)s leading to new pi-system-expanded chromophores are described. The first route follows a two-step approach: Suzuki coupling of bromo-substituted perylenebis(dicarboximide) with 2-bromophenylboronic acid, followed by palladium-catalysed dehydrobromination. The second route is best described as a palladium-assisted cycloaddition of benzyne, formed in situ, to the bay-region of the bromo-substituted rylene core. Two new types of core-expanded rylene dyes were synthesised: yellow dibenzocoronenebis(dicarboximide)s, absorbing at 490 nm, and a green dinaphthoquaterrylenebis(dicarboximide), which absorbs at 700 nm. These new chromophores are characterised by significant hypsochromic shifts of absorption, compared to their parent rylenebis(dicarboximide)s, excellent photostabilities and high fluorescence quantum yields.

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Design of Near-Infrared Dyes Based on π-Conjugation System Extension 2. Theoretical Elucidation of Framework Extended Derivatives of Perylene Chromophore

Cited by 70 publications

References 65 publications

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

Hole‐Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene

Control of the Interactions in Multichromophores: Novel Concepts. Perylene Bis‐imides as Components for Larger Functional Units

Novel Core‐Expanded Rylenebis(Dicarboximide) Dyes Bearing Pentacene Units: Facile Synthesis and Photophysical Properties

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