Toward an n-Type Molecular Wire: Electron Hopping within Linearly Linked Perylenediimide Oligomers

Wilson, Thea M.; Tauber, Michael J.; Wasielewski, Michael R.

doi:10.1021/ja902258g

Cited by 94 publications

(76 citation statements)

References 67 publications

(120 reference statements)

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“…Dimer 2 sC À also has hfccs not much larger than those of the monomer, but its spectrum is more complex, with each proton resonance further split. This additional splitting is a common ENDOR spectral feature when PDIC À is asymmetric, [28] and is consistent with the asymmetric environment of the adjacent P moieties in 2 s. The ENDOR spectrum of 3C À does not exhibit a reduction in the magnitude of the hfccs by a factor of three relative to 1C À . Rather, the spectrum of 3C À has an overall spectral width that is narrower than that observed for the monomer, but broader than that observed in the spectra of the dimers, with indistinct spectral features.…”

Section: Mhz (1-h 6-h 7-h 12-h) and 28 Mhz (2-h 5-h 8-h 11-h)supporting

confidence: 70%

“…[28,29] In the next-larger system, 4C À , electron hopping at a rate above 10 7 s À1 was only observed among three of the four P moieties. Again, the fact that not all P units were involved in electron hopping could be due to a difference in the LUMO energies of the P moieties of the tetramer stack.…”

Section: Mhz (1-h 6-h 7-h 12-h) and 28 Mhz (2-h 5-h 8-h 11-h)mentioning

confidence: 90%

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Electron Hopping among Cofacially Stacked Perylenediimides Assembled by Using DNA Hairpins

et al. 2010

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The self-assembly of redox-active molecules into ordered arrays capable of rapid, long-distance charge transport is important for the development of functional nanomaterials for organic electronics. In this regard, DNA shows great promise as a structural scaffold for the helical arrangement of chromophores and other (semi)conducting materials. [1][2][3] Base substitutions and modifications, sugar modifications, and noncovalent interactions have all been used for the construction of such DNA-based structures. Perylenediimides (PDIs), which have the advantages of strong absorptivity, high fluorescence quantum yields, high photochemical and thermal stability, strong hydrophobic p-p stacking interactions, and semiconducting properties, have been incorporated in a variety of structures. [4][5][6][7][8][9][10][11][12][13][14][15][16] Recently, Wagner and Wagenknecht [10] reported the preparation of a PDI derivative, P (Figure 1), which is readily incorporated into an oligonucleotide and serves as a base-pair surrogate when located opposite an abasic site in a duplex structure. The incorporation of P in opposite complementary oligonucleotides has been shown to result in the formation of stable duplexes in which the P units are located in a zipperlike fashion within the hydrophobic interior of the resulting duplex. [5,17] The stacking of P units within the duplex resulted in an excimer-like state following photoexcitation. [16] We report herein the results of our investigation of intramolecular electron hopping within a series of synthetic DNA hairpins 1-4 (Figure 1). These hairpins possess compact 3'-CCA loop regions connecting poly(T)-poly(A) stems containing a single P moiety located opposite an abasic site (1), two P moieties located opposite abasic sites and attached either to the same strand (in 2 s) or to opposite strands (in 2 o), or three or four P moieties positioned adjacent to one another but on opposite strands in a zipperlike fashion (in 3 and 4). The EPR spectra of the singly reduced duplexes were consistent with electron hopping between two sites in both dimers (the hairpins containing two P moieties) and the trimer 3, and among three sites in the tetramer 4. Herein, we discuss the origin and implications of partial electron sharing.Oligonucleotides containing P were synthesized by the method of Wagner and Wagenknecht; [10] the CCA linker in hairpins 1-4 has been employed previously in the synthesis of stable minihairpins. [13,17,18] The characterization of 1-4, including mass spectrometry and circular dichroism (CD), is described in the Supporting Information.An intensity reversal was observed in the UV/Vis absorption spectra for the 0!0 and 0!1 transitions in 2-4 with respect to those of 1 (Figure 2). This result indicates that the p-stacked P chromophores are exciton-coupled. [19][20][21] Moreover, the A 0!0 /A 0!1 ratio for the vibronic bands decreased as the number of P units increased, and there was a notable difference between dimers 2 s and 2 o, presumably as a result of the conformational changes...

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Section: Mhz (1-h 6-h 7-h 12-h) and 28 Mhz (2-h 5-h 8-h 11-h)supporting

confidence: 70%

Section: Mhz (1-h 6-h 7-h 12-h) and 28 Mhz (2-h 5-h 8-h 11-h)mentioning

confidence: 90%

Electron Hopping among Cofacially Stacked Perylenediimides Assembled by Using DNA Hairpins

et al. 2010

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“…Perylene bisimides (PBIs) and their related derivatives have continuously received significant attention due to their potential applications in molecular optoelectronic devices, such as organic field-effect transistors (OFETs) [1,2,3,4,5,6], photovoltaic cells [7,8,9,10,11,12,13,14,15,16], light-emitting diodes [17,18,19,20,21], light-harvesting arrays [22,23], photochromic materials [24,25], molecular wires [26,27] and LCD color filters [28,29]. In addition, PBIs have been used as building blocks to construct supramolecular or artificial photosynthetic systems [30,31,32,33].…”

Section: Introductionmentioning

confidence: 99%

Green Perylene Bisimide Dyes: Synthesis, Photophysical and Electrochemical Properties

Chang¹,

Tsai²,

Chen³

2014

Materials

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Three asymmetric amino-substituted perylene bisimide dyes with different n-alkyl chain lengths (n = 6, 12, or 18), 1-(N,N-dialkylamino)perylene bisimides (1a-1c), were synthesized under mild condition in high yields and were characterized by 1 H NMR, 13C NMR (nuclear magnetic resonance), HRMS (High Resolution Mass Spectrometer), UV-Vis and fluorescence spectra, as well as cyclic voltammetry (CV). These molecules show intense green color in both solution and solid state and are highly soluble in dichloromethane and even in nonpolar solvents, such as hexane. The shapes of the absorption spectra of 1a-1c in solid state and in solution were found to be virtually the same, indicating that the long alkyl chains could efficiently prevent aggregation. They exhibit a unique charge transfer emission in the near-infrared region, of which the peak wavelengths show strong solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1-aminoperylene bisimide (2). Furthermore, all of the compounds exhibit two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory (DFT) calculations performed on these dyes are reported in order to rationalize their molecular structures and electronic properties.

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“…Due to these desirable attributes, PDIs and PTCDs have been used in a variety of applications in the field of organic electronics and optical devices, such as organic light-emitting diodes (OLEDs) [17,18], organic field-effect transistors (OFETs) [19,20], photochromic materials [21,22], molecular wires [23,24], LCD color filters [25,26], light-harvesting arrays [27,28] and organic solar cells (OSCs) [29,30,31,32]. PDIs and PTCDs have also been utilized in many other applications such as artificial photosynthetic systems through controlled supramolecular architectures via intermolecular π-π stacking [33,34].…”

Section: Introductionmentioning

confidence: 99%

1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties

2015

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1,6- and 1,7-regioisomers of diamino-substituted perylene tetracarboxylic dianhydrides (PTCDs) with different n-alkyl chain lengths (n = 6, 12 or 18) were synthesized and characterized by NMR spectroscopy and high-resolution mass spectrometry. These dyes are highly soluble in most organic solvents and even in nonpolar solvents, such as hexane. To the best of our knowledge, this is the first time the 1,6-diamino-substituted PTCDs (2a–2c) have been obtained in pure form. The regioisomers 1a–1c (1,7-) and 2a–2c (1,6-) exhibit significant differences in their optical characteristics. In addition to the longest wavelength absorption band at around 674 nm, 2a–2c exhibit another shoulder band at ca. 600 nm, and consequently, cover a large part of the visible region relative to those of 1a–1c. Upon excitation, 2a–2c also show larger dipole moment changes than those of 1a–1c; the dipole moments of all compounds have been estimated using Lippert–Mataga equation. Moreover, all the dyes show a unique charge transfer emission in the near-infrared region, of which the peak wavelengths exhibit strong solvatochromism. They all exhibit one irreversible one-electron oxidation and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to rationalize their electronic structure and optical properties.

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Toward an n-Type Molecular Wire: Electron Hopping within Linearly Linked Perylenediimide Oligomers

Cited by 94 publications

References 67 publications

Electron Hopping among Cofacially Stacked Perylenediimides Assembled by Using DNA Hairpins

Electron Hopping among Cofacially Stacked Perylenediimides Assembled by Using DNA Hairpins

Green Perylene Bisimide Dyes: Synthesis, Photophysical and Electrochemical Properties

1,6- and 1,7-Regioisomers of Highly Soluble Amino-Substituted Perylene Tetracarboxylic Dianhydrides: Synthesis, Optical and Electrochemical Properties

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