Electron Hopping in π-Stacked Covalent and Self-Assembled Perylene Diimides Observed by ENDOR Spectroscopy

Tauber, Michael J.; Kelley, Richard F.; Giaimo, Jovan M.; Rybtchinski, Boris; Wasielewski, Michael R.

doi:10.1021/ja057031k

Cited by 142 publications

(130 citation statements)

References 33 publications

(63 reference statements)

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“…attached to steroids by Louw et al) perylene-3,4:9,10-tetracarboxylic acid-3,4-anhydride-9,10-imide 8 [19] was treated with 3-iodoaniline to obtain PBI 9 in a yield of 97 % in analogy to the literature-known reaction of symmetric 3,5-diiodoaniline with 8 affording PBI 12,…”

Section: Synthesismentioning

confidence: 99%

Phenylene Ethynylene‐Tethered Perylene Bisimide Folda‐Dimer and Folda‐Trimer: Investigations on Folding Features in Ground and Excited States

Fimmel

Son

Sung

et al. 2014

Chemistry A European J

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In this work, we have elucidated in detail the folding properties of two perylene bisimide (PBI) foldamers composed of two and three PBI units, respectively, attached to a phenylene ethynylene backbone. The folding behaviors of these new PBI folda-dimer and trimer have been studied by solvent-dependent UV/Vis absorption and 1D and 2D NMR spectroscopy, revealing facile folding of both systems in tetrahydrofuran (THF). In CHCl3 the dimer exists in extended (unfolded) conformation, whereas partially folded conformations are observed in the trimer. Temperature-dependent (1) H NMR spectroscopic studies in [D8 ]THF revealed intramolecular dynamic processes for both PBI foldamers due to, on the one hand, hindered rotation around CN imide bonds and, on the other hand, backbone flapping; the latter process being energetically more demanding as it was observed only at elevated temperature. The structural features of folded conformations of the dimer and trimer have been elucidated by different 2D-NMR spectroscopy (e.g., ROESY and DOSY) in [D8 ]THF. The energetics of folding processes for the PBI dimer and trimer have been assessed by calculations applying various methods, particularly the semiempirical PM6-DH2 and the more sophisticated B97D approach, in which relevant dispersion corrections are included. These calculations corroborate the results of NMR spectroscopic studies. Folding features in the excited states of these PBI foldamers have been characterized by using time-resolved fluorescence and transient absorption spectroscopy in THF and CHCl3 , exhibiting similar solvent-dependent behavior as observed for the ground state. Interestingly, photoinduced electron transfer (PET) process from electron-donating backbone to electron-deficient PBI core for extended, but not for folded, conformations was observed, which can be explained by a fast relaxation of excited PBI stacks in the folded conformation into fluorescent excimer states.

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Section: Synthesismentioning

confidence: 99%

Phenylene Ethynylene‐Tethered Perylene Bisimide Folda‐Dimer and Folda‐Trimer: Investigations on Folding Features in Ground and Excited States

Fimmel

Son

Sung

et al. 2014

Chemistry A European J

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“…Coherent band model [13][14] and incoherent hopping model [15][16] are the two classical theoretical models in describing the charge transport process in the solid materials. The coherent band model was usually applied in system with strong interaction between two neighbor molecules while the incoherent hopping model was usually applied to deal with intermolecular interactions of which most are non-covalent interactions such as hydrogen bonding, π-stacking, polar-nonpolar.…”

Section: Theoretical Modelsmentioning

confidence: 99%

Theoretical Investigation on Charge Transfer Properties of 1,3,5-Tripyrrolebenzene (TPB) and its Derivatives with Electron-withdrawing Substituents

Hu¹,

Yin²,

Chaitanya³

et al. 2016

Croat. Chem. Acta

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Abstract:The electronic structures and charge transport properties of 1,3,5-tripyrrolebenzene (TPB) and its substituted derivatives with -F and -CN groups have been investigated by DFT calculations in combination with the Marcus hopping model. The dimer geometry was optimized by density functional theory method with dispersion force correction being included (DFT-D). Consequently, the charge transfer integral was evaluated. The calculation results show that the introduction of electron-withdrawing substituents does not significantly change the bond lengths and molecular symmetry of TPB, but lower the coplanarity between the pyrrole and benzene rings, especially in the case of CN substitution. Meanwhile, the introduction of electron-withdrawing groups can decrease the energy of the frontier molecular orbital and enhance the air stability. Fluorination makes the λe increase obviously while cyanation dose not. Generally speaking, the λe values of the title compounds are larger than their λh. Except for compounds 6 and 9, all others keep the face to face packing or have a slight slip in dimers, but the center of mass distances increase after fluorination or cyanation due to the distortion of the monomer's coplanarity. The predicted quasi-one-dimensional electron mobility of the dimers is up to 0.433 cm 2 ·V -1 ·s -1 at 298.15 K. The electron injection barriers of 2 and 7 are lower than that of TPB. The TPB derivatives of 1, 2, and 7 are potential n-channel materials with the high electron mobility.

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“…Photoexcitation of exTTF-oPPE-C 60 leads to the following features: a transient photoproduct with maxima at 660 and 1000 nm, which are unambiguously attributed to the photolytically generated radical-ion-pair state, [exTTFC + -oPPE-C 60 C À ]. Both charge-separation and charge-recombination processes give rise to a molecular-wire behaviour of the oPPE moiety with an attenuation factor (b) of (0.2 AE 0.05) between the electron donor and acceptor units by means of the bridge orbitals [2] and 3) a small attenuation factor (b).…”

Section: Introductionmentioning

confidence: 99%

p‐Phenyleneethynylene Molecular Wires: Influence of Structure on Photoinduced Electron‐Transfer Properties

Wielopolski

Atienza

Clark

et al. 2008

Chemistry A European J

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A series of donor-acceptor arrays (exTTF-oPPE-C60) containing pi-conjugated oligo(phenyleneethynylene) wires (oPPE) of different length between pi-extended tetrathiafulvalene (exTTF) as electron donor and fullerene (C60) as electron acceptor has been prepared by following a convergent synthesis. The key reaction in these approaches is the bromo-iodo selectivity of the Hagihara-Sonogashira reaction and the deprotecting of acetylenes with different silyl groups to afford the corresponding donor-acceptor conjugates in moderate yields. The electronic interactions between the three electroactive species were determined by using UV-visible spectroscopy and cyclic voltammetry. Our studies clearly confirm that, although the C60 units are connected to the exTTF donor through pi-conjugated oPPE frameworks, no significant electronic interactions are observed in the ground state. Theoretical calculations predict how a simple exchange from C=C double bonds (i.e., oligo(p-phenylenevinylene) to C triple chemical bond C triple bonds (i.e., oPPE) in the electron donor-acceptor conjugates considerably alters long-range electron transfer. Photoexcitation of exTTF-oPPE-C60 leads to the following features: a transient photoproduct with maxima at 660 and 1000 nm, which are unambiguously attributed to the photolytically generated radical-ion-pair state, [exTTF*+-oPPE-C60*]. Both charge-separation and charge-recombination processes give rise to a molecular-wire behaviour of the oPPE moiety with an attenuation factor (beta) of (0.2+/-0.05) A(-1).

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Electron Hopping in π-Stacked Covalent and Self-Assembled Perylene Diimides Observed by ENDOR Spectroscopy

Cited by 142 publications

References 33 publications

Phenylene Ethynylene‐Tethered Perylene Bisimide Folda‐Dimer and Folda‐Trimer: Investigations on Folding Features in Ground and Excited States

Phenylene Ethynylene‐Tethered Perylene Bisimide Folda‐Dimer and Folda‐Trimer: Investigations on Folding Features in Ground and Excited States

Theoretical Investigation on Charge Transfer Properties of 1,3,5-Tripyrrolebenzene (TPB) and its Derivatives with Electron-withdrawing Substituents

p‐Phenyleneethynylene Molecular Wires: Influence of Structure on Photoinduced Electron‐Transfer Properties

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