Band-shape analysis of the charge-transfer fluorescence in barrelene-based electron donor-acceptor compounds

Cortes, José Apolinar; Heitele, H.; Jortner, Joshua

doi:10.1021/j100061a006

Cited by 151 publications

(161 citation statements)

References 1 publication

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“…In general, -F substituent result in an obviously increasing on λe except for 8 [50,48] and the introduced substituent groups can bring in more vibrational modes of geometric relaxation that will lead to λe increase from the aspect of normal-mode (MN). [17,48,53,54] The triple bond of -CN which was connected into the original molecular π-conjugate system makes the conjugate system a further expanded. And the injected electron can locate on a wider space, this can help to decrease the λe.…”

Section: Frontier Molecular Orbital Ionization Potentials Electron mentioning

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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Section: Frontier Molecular Orbital Ionization Potentials Electron mentioning

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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“…This calculation was made following the procedures introduced by Meyer and co-workers. [10] Thus, the reduced emission spectrum, [26,27] as displayed in wavenumbers, was deconvoluted into the minimum number of Gaussian-shaped components of equal half-width (Dn 1/2 ). The peak maximum (E 0 ) of the highest energy Gaussian component is taken to represent the energy difference between 0,0 vibronic levels in the triplet and ground states while the energy spacing between adjacent Gaussian components (" hw) is attributed to the averaged medium frequency vibrational mode coupled to the MLCT triplet state.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Triplet Energy Transfer in Pyrene-Metal Polypyridine Dyads: A Strategy for Extending the Triplet Lifetime of the Metal Complex

et al. 1999

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A series of photoactive dyads bearing pyrene and metal (M Ru II ) or Os II ) tris(2,2'-bipyridine) terminals bridged by an ethynylene or Pt II bis(sacetylide) moiety has been synthesized and investigated by transient spectroscopy. Selective excitation into the terminal metal complex is possible in each case and generates the lowest energy, excited triplet state localized on that molecular fragment. For both Os II -based dyads, the triplet state is unperturbed by the appended pyrene unit and the observed photophysical properties can be understood within the framework of the energy-gap law. The triplet state localized on the metal complex in the two Ru II -based dyads is involved in reversible energy transfer with the triplet associated with the pyrene unit, which is situated at slightly lower energy. When the terminal metal complex is a Ru II bis(2,2':6',2''-terpyridyl) fragment, however, the triplet levels are inverted such that the pyrene-like triplet state lies slightly above that of the metal complex. Kinetic spectrophotometry has allowed determination of the various rate constants and energy gaps and, on the basis of nonadiabatic electron-transfer theory, it appears that the central Pt bis(sacetylide) unit is a much inferior electronic conductor than is a simple ethynylene group. Reversible energy transfer of this type greatly prolongs the triplet lifetime of the Ru II tris(2,2'-bipyridyl) fragment. For example, equilibration between the triplet states is achieved within 10 ps for the ethynylenebridged dyad while the equilibrium mixture decays with a lifetime of about 40 ms in deoxygenated acetonitrile at room temperature.

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“…These results can be compared with the literature results for nonpolar liquids, which are summarized in Table 1. The previous results are smaller than either curve given in Fig 3b except the resultsby Cortes et aL [24] (The interpretation of those results is uncertain, in that the authors refer to these values as unphysically large.) There are several possible explanations for the relatively large value of E~determined from the present experiment.…”

Section: 30~-1mentioning

confidence: 61%

Solvent reorganization energies measured by an electron transfer reaction in supercritical ethane

Takahashi

Sawamura

Jonah

1998

The Journal of Supercritical Fluids

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The intermolecular electron transfer reaction between a biphenyl anion and pyrene in supercntical ethane was studied using pulse radiolysis. Second-order electron trausfer rates were found to be of the order of 1011M-1 s-l. The rate constants appear to be approximately constant over the pressure range 55-133 bar. Two possibilities are discussed that could explain the present results: solvent clustering; or a dependence of the solvent reorganization energy on pressure. Reorganization energies Er of non-polar supercritical ethane were estimated from the observed rate constant using the modified Marcus equation. Er may be larger than normally expected for nonpolar solvents because of density fluctuations. .-Introduction It is well known that density fluctuations [1] and clustering of solvent molecules [2][3][4][5][6][7][8] are observed in supercritical fluids(SCFs). The local density of SCFS around a solute may be significantly greater than the bulk density of fluid not only in polar fluids [9] but also in non-polar fluids [ 10]. The number of molecules around a solute is sibtificantly changed near the critical pressure [11]. RecentIy,Matyushov and Schrnid[12] have theoretically studied solvent reorganization energy Er arising from charge separation and recombination reactions in non-polar fluids. According to their results, the Er in non-polar solvent is not zero but can be represented as the sum of two terms that arise from liquid polarization and density reorganization, with the latter component being of much greater importance.For this reason we felt that electron transfer (ET) reactions in non-polar SCFS might show a new aspect of the solvent reorganization energy in non-polar fluids. While radical reactions have been studied in SCFS[13-16 for example], we are unaware of any ET reactions that have been studied in SCFS.In this work we present the intermolecular ET reactions in non-polar SCFS. We chose to use ethane as a non-polar solvent because it was relatively unreactive to the ions formed and a supercritical fluid could be formed conveniently. Biphenyl anion and pyrene were used as au electron donor and acceptor, respectively. The solvent reorganization energies were estimated using the measured ET rates. Materials and MethodsHi~h messure eauir)ment Experiments were run with a cylindrical stainless-steel high pressure cell (Takagi equipment CO., LTD., 4 cm in O.D., 9.5 cm in length). The 1 cm thick supra.silwindows were mounted to the cell using Teflon o-rings. The optical path length is 6 cm and the cell capacity is 4.2 cm3. The temperature of the cell was maintained constant to~0.1'C at 35°C (A 0.5"C) using an Omega temperature controller (Model CNIOOIRTD), a cartridge heater and a platinum resistance thermometer. The thermometer was installed into the cell so that it is in contact with the fluid. Pressures were generated using a JASCO HPLC pump (Model PU-980, with a flow controller and pressure sensor). The fluid pressure was monitored with Cole-Parrner digital pressure meter (Model 7350-38) and pressu...

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Band-shape analysis of the charge-transfer fluorescence in barrelene-based electron donor-acceptor compounds

Cited by 151 publications

References 1 publication

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

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

Intramolecular Triplet Energy Transfer in Pyrene-Metal Polypyridine Dyads: A Strategy for Extending the Triplet Lifetime of the Metal Complex

Solvent reorganization energies measured by an electron transfer reaction in supercritical ethane

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