Theoretical discussions on electron transport properties of perylene bisimide derivatives with different molecular packings and intermolecular interactions

Geng, Yun; Wang, Jianping; Wu, Shui‐Xing; Li, Haibin; Yu, Fei; Yang, Guochun; Gao, Hongze; Su, Zhong‐Min

doi:10.1039/c0jm02119a

Cited by 88 publications

(83 citation statements)

References 67 publications

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“…[85][86][87][88][89] Furthermore, ohmic contact is also expected for (CN 2 PhCC) 2 Electron injection efficiency is also related to vertical electron affinity, VEA, which increases between 0.2 and 0.4 eV with respect to Ar 2 Tz derivatives, due to the presence of the ethynylene groups (see Table 3). 17 The adiabatic electron affinity, AEA, also increases of 0.5 -0.6 eV for the tetrahalogenated derivatives and 1.1 eV for the cyanide derivative with respect to (PhCC) 2 71,72 and lie on the range of the values experimentally determined for common n-type organic semiconductors such as N,N'-substituted arylenediimides and perfluoroalkyl oligothiophenes. 73 Regarding electron injection, ohmic contact can be expected for all the studied (ArCC) 2 Tz derivatives with respect to some of the common electrodes used …”

Section: Acs Paragon Plus Environmentmentioning

confidence: 70%

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

et al. 2015

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We theoretically describe in this work the n-type semiconducting behavior of a set of bis(arylene-ethynylene)-s-tetrazines ((ArCC) 2 Tz), by comparing their electronic properties with those of their parent diaryl-s-tetrazines (Ar 2 Tz) after the introduction of ethynylene bridges. The significantly reduced internal reorganization energy for electron transfer is ascribed to an extended delocalization of the LUMO for (ArCC) 2 Tz as opposite to that for Ar 2 Tz, which was described mostly localized on the s-tetrazine ring. The largest electronic coupling and the corresponding electron transfer rates found 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 for bis(phenyl-ethynylene)-s-tetrazine, as well as for some halogenated derivatives, are comparable to those reported for the best performing n-type organic semiconductors materials such as diimides and perylenes. The theoretical mobilities for the studied compounds turn out to be in the range 0.3 -1.3 cm 2 V −1 s −1 , close to values experimentally determined for common n-type organic semiconductors used in real devices. In addition, ohmic contacts can be expected when these compounds are coupled to metallic cathodes such as Na, Ca and Sm. For these reasons, the future application of semiconducting bis(phenyl-ethynylene)-s-tetrazine and its fluorinated and brominated derivatives in optoelectronic devices is envisioned.

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Section: Acs Paragon Plus Environmentmentioning

confidence: 70%

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

et al. 2015

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“…Three possible explanations for this trend are: a) A more aggregated film has a higher extent of extended π-π conjugation, and this may lower the reorganization energy for electron transfer. 16,55,59,60 However, intermolecular coupling sufficiently strong to significantly reduce the reorganization energy might also be expected to be accompanied by a shift in redox potential; e.g., a phthalocyanine dimer is more readily oxidized than the corresponding monomer. 16 The data in Tables 1 and S3 show that the E 0 ' values for the four types of PDI molecules are statistically equivalent; thus it unlikely that differences in reorganization energy are the source of the difference in the k s,opt values in Table 2.…”

Section: Electron-transfer Kinetics At the Pdi Film/ito Interfacementioning

confidence: 99%

Influence of Molecular Aggregation on Electron Transfer at the Perylene Diimide/Indium-Tin Oxide Interface

Zheng

Jradi

Parker

et al. 2016

ACS Appl. Mater. Interfaces

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Chemisorption of an organic monolayer to tune the surface properties of a transparent conductive oxide (TCO) electrode can improve the performance of organic electronic devices that rely on efficient charge transfer between an organic active layer and a TCO contact. Here a series of perylene diimides (PDIs) was synthesized and used to study relationships between monolayer structure/properties and electron transfer kinetics at PDI-modified indium tin oxide (ITO) electrodes. In these PDI molecules, one of the imide substituents is a benzene ring bearing a phosphonic acid (PA) and the other is a bulky aryl group that is twisted out of the plane of the PDI core. The size of the bulky aryl group and the substitution of the benzene ring bearing the PA were both varied which altered the extent of aggregation when these molecules were absorbed as monolayer films (MLs) on ITO, as revealed by both attenuated total reflectance (ATR) and total internal reflection fluorescence (TIRF) spectra. Polarized ATR measurements indicate that in these MLs, the long axis of the PDI core is tilted at an angle of 33˚-42˚ relative to the surface normal; the tilt angle increased as the degree of bulky substitution increased. Rate constants for electron transfer (k s,opt ) between these redox-active modifiers and ITO were determined by potential-modulated ATR spectroscopy. As the degree of PDI aggregation was reduced, k s,opt declined which is attributed to a reduction in the lateral electron self-exchange rate between adsorbed PDI molecules, as well as the heterogeneous conductivity of the ITO electrode surface. Photoelectrochemical measurements using a dissolved aluminum phthalocyanine as an electron donor showed that ITO modified with any of these PDIs is a more effective electron-collecting electrode than bare ITO.

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“…This model has been applied successfully in many earlier studies. [50][51][52][53][54] Here, the energy required (l 1 ) in eV for the reorganization of the neutral geometry to the cation geometry upon removal of an electron and the energy required (l 2 ) to reorganize the obtained cation geometry back to a neutral state upon re-accepting an electron added up, give the total reorganization energy (l + ) of the molecule when the hole is being transported. In a similar fashion, the reorganization energy (l À ) of the neutral to the anion (l 3 ) and back (l 4 ) should be useful in understanding the electron transport.…”

Section: Reorganization Energiesmentioning

confidence: 99%

“…[50][51][52][53][54] The reorganization energy consists of both intramolecular and intermolecular contributions. [66] The intramolecular contribution is correlated to the geometry changes of the molecule and the intermolecular contributions are correlated to the polarization of the surrounding molecules upon oxidation/reduction.…”

Section: Reorganization Energiesmentioning

confidence: 99%

Comparative Study of the Semiconducting Properties of Benzothiadiazole and Benzobis(thiadiazole) Derivatives Using Computational Techniques

Thomas

Bhanuprakash

2012

ChemPhysChem

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Recent literature reports indicate that derivatives of benzothiadiazole (BT) and benzobis(thiadiazole) (BBT), which differs from BT by an extra thiadiazole ring, exhibit good semiconducting properties, such as high electron mobility and low-lying lowest unoccupied molecular-orbital (LUMO) levels. In this study herein, computational techniques like density functional theory (DFT), spin-flip DFT and valence-bond methods are used to analyze the semiconducting properties of these molecules. Calculations at the B3LYP/cc-pVTZ level reveal that all the BBT molecules, including the bare BBT ring, have lower lying LUMO energies (3.70-4.11 eV) compared to the BT derivatives (2.56-3.41 eV) with similar substitution. The reorganization energies (λ(+)/λ(-)) obtained at this level of theory of the BT derivatives are around (225-333)/(246-315) meV, while BBT derivatives have much smaller reorganization energies and these are in the range of (129-259)/(150-230) meV. We observe that the different behavior of BBT is due to the inherited biradicaloid character from the parent molecule tetramethylenebenzene (TMB), a disjoint non-Kekule biradical having non-bonding molecular orbitals (NBMOs) as the highest occupied molecular orbital (HOMO) and LUMO. Additionally, the perturbation of the orbitals of the biradical TMB to obtain BBT is the major cause for the BBT derivatives to have a larger electron affinity (EA) and a smaller HOMO-LUMO gap (HLG) compared to BT derivatives.

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Theoretical discussions on electron transport properties of perylene bisimide derivatives with different molecular packings and intermolecular interactions

Cited by 88 publications

References 67 publications

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

Influence of Molecular Aggregation on Electron Transfer at the Perylene Diimide/Indium-Tin Oxide Interface

Comparative Study of the Semiconducting Properties of Benzothiadiazole and Benzobis(thiadiazole) Derivatives Using Computational Techniques

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