Resonant capture of low-energy electrons by molecules of phthalide derivatives

Zykov, B. G.; Vasil'ev, Yu. V.; Fal’ko, Vladimir I.; Лачинов, А. Н.; Khvostenko, V. I.; Gileva, N. G.

doi:10.1134/1.567237

Cited by 20 publications

(11 citation statements)

References 10 publications

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“…The least polarity (5.6 D) has a sawtooth shaped molecule with phthalide groups turned in different directions, dipole moment of a helical molecule with the same phthalide groups arrangement is almost twice higher (10.5 D). The ionisation potential of a helical free molecule from three units is 7.11 eV (adiabatic) and 7.24 eV (vertical), the external electron attachment energy is nearby 0.8 eV that is good correlated with experimental data for diphenyl phthalide [21].…”

Section: Resultssupporting

confidence: 69%

Polydiphenylenephthalide: Optical Spectroscopy and DFT Calculations

Кухто

Kukhta²,

Салазкин³

2011

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The results of spectral and luminescent studies of polydiphenylenphthalide (PDF) solutions and thin films as well as molecule structure and its energy levels DFT modelling within the Gaussian-03 software package are presented. It is shown that structural unit (diphenylenephthalide) can form four polymer conformations with a similar energy gap. The most probable polymer conformation is the spiral cis-form with phthalide groups turned in opposite directions. At long-wave optical transition the electronic density moves on a chain of a molecule from diphenyl part to somehow distant phthalide one. Fluorescence excitation spectra reveal a transition band on a long-wave tail of the absorption spectrum. Spectral and time measurements of the luminescence allow to assume the presence of conformation transformations of PDF molecule under its optical excitation.

http://dx.doi.org/10.5755/j01.ms.17.3.591

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Section: Resultssupporting

confidence: 69%

Polydiphenylenephthalide: Optical Spectroscopy and DFT Calculations

Кухто

Kukhta²,

Салазкин³

2011

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http://dx.doi.org/10.5755/j01.ms.17.3.591

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“…11 Opening of the lactone ring in Pd moiety due to, e.g., effect of pressure, electric field or heat, was claimed to be the reason for a dielectric-to-metal transition in poly(3,3 0 -phthalidylidene-4,4 0 -biphenylene) polymers (PPB) giving rise to unusual electrophysical properties of these materials. 12 Adiabatic photodissociation of C-O bond in lactone ring of phthalide moiety was reported to be responsible for dual luminescence of lactonic forms of rhodamines. 13,14 Recently, phthalide was used as an efficient electron acceptor in photoinduced ultrafast charge separation process in malachite green lactone and in phenolphthalein, 15,16 and its 6-dimethylamino derivative has been found to play a crucial role in photophysics of crystal violet lactone.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced intramolecular charge transfer to meta position of benzene ring in 6-aminophthalides

Karpiuk

Svartsov

Nowacki

2005

Phys. Chem. Chem. Phys.

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Substitution of non-fluorescent phthalide (Pd) with amino group at meta (6) position in relation to the electron-accepting part of the lactone ring completely changes Pd photophysics: a new long-wavelength absorption band arises and the molecule becomes highly fluorescent. The experimental data and the analysis of vertical electronic transitions with TDDFT method indicate that the first absorption band in 6-aminophthalides (6-APds) comprises a single CT transition to the S1 state. Almost equal absorption and emission transition dipole moments indicate that S0 <--> S1 transition in all 6-APds is not affected by any mixing with other electronic states, the excited-state vibrational relaxation is not accompanied by significant conformational changes and the Stokes shifts reflect mainly solvation energetics of these molecules. Excited state dipole moments obtained from solvatochromic plots and from CASSCF calculations confirm large charge displacement from amino group towards the meta position of the benzene ring upon excitation of 6-APds to S1 state. Long fluorescence lifetimes and high fluorescence quantum yields demonstrate efficient and stable excited state charge separation in 6-APds. Taken together with sensitivity of 6-APds to polarity and proticity of the environment these properties make them good candidates for fluorescent probes of long-time scale molecular dynamics.

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Section: Introductionmentioning

confidence: 97%

“…Moreover, these compounds have recently come under scrutiny because of their estrogenic effects and are, therefore, of some concern as environmental agents for which new analytical techniques would be desirable. The investigation of phthalates by negative ion mass spectrometry seems not to have received much attention, but studies on the interaction of low-energy electrons with phthalic anhydride and aryl phthalides have been reported. , …”

Section: Introductionmentioning

confidence: 99%

“…The investigation of phthalates by negative ion mass spectrometry seems not to have received much attention, but studies on the interaction of low-energy electrons with phthalic anhydride 12 and aryl phthalides have been reported. 13,14 Electron Monochromator-Mass Spectrometer Instrument. The EM-MS system consists of an in-house-constructed monochromator source interfaced to a Hewlett-Packard 5982A quadrupole mass spectrometer.…”

Section: Introductionmentioning

confidence: 99%

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Steric Effects on Gas-Phase Negative Ion Resonances of Phthalates

and

Deinzer

1999

J. Am. Chem. Soc.

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The interaction of low-energy electrons with eight phthalates was studied using an electron monochromator-mass spectromer (EM-MS). Each phthalate captures electrons of discrete energy to yield negative ions by resonance or dissociative electron capture. Two negative ion resonances are generally observed for each ion. Electrons with energies of ∼0.6 and ∼1.1 eV result in maximum molecular ion intensity for o-phthalates, while higher energy electrons produce (M-R 1 ) -, (M-R 1 -R 2 + H) -, and phthalic anhydride ions. m-Dimethyl phthalate yields a molecular ion with electrons of energies 0.19 and 0.87 eV, but no fragment ions. Electron attachment energies calculated with the HF/D95//HF/6-31G basis set and a scaling constant are in reasonable agreement with the experimental values for the first molecular ion state of each phthalate. Semiemperical calculations show that the optimum geometry for m-dimethyl phthalate results when both ester groups are coplanar with the benzene ring, while steric interactions force the ester groups of o-phthalates into noncoplanar orientations relative to the benzene ring. It is suggested that this geometry leads to efficient π*-σ* orbital interaction in the transient radical anion and facile fragmentation, producing product anions and radicals. Larger R groups result in a lowering of the electron energies required to produce (M-R 1 ) -, a result which is interpreted on the basis of greater steric compression of the ester groups in the transient negative ion.

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Resonant capture of low-energy electrons by molecules of phthalide derivatives

Cited by 20 publications

References 10 publications

Polydiphenylenephthalide: Optical Spectroscopy and DFT Calculations

Polydiphenylenephthalide: Optical Spectroscopy and DFT Calculations

Photoinduced intramolecular charge transfer to meta position of benzene ring in 6-aminophthalides

Steric Effects on Gas-Phase Negative Ion Resonances of Phthalates

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