Experimental and theoretical study of the structure of N,N-dimethyl-4-nitroaniline derivatives as model compounds for non-linear optical organic materials

Borbulevych, O.Y.; Clark, Ronald D.; Romero, A.; Tan, Li; Antipin, M. Yu.; Нестеров, В. Н.; Cardelino, Beatriz H.; Moore, Craig E.; Sanghadasa, Mohan; Timofeeva, Tatiana V.

doi:10.1016/s0022-2860(01)00642-1

Cited by 35 publications

(21 citation statements)

References 27 publications

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“…This shows that contribution of the quinoid form, resulted from the intramolecular groundstate charge transfer, is highest and lowest in 1 and 4, respectively. This bond in N,N-dimethyl-p-nitroaniline [33] is much longer than that in 1. On the other hand, the C-NMe 2 bond in N,N-dimethyl-p-nitroaniline [33] and these in 3 and 4 are comparable.…”

Section: Resultsmentioning

confidence: 80%

“…This bond in N,N-dimethyl-p-nitroaniline [33] is much longer than that in 1. On the other hand, the C-NMe 2 bond in N,N-dimethyl-p-nitroaniline [33] and these in 3 and 4 are comparable. It is also true for 2 and 4-[(1E)-2-dimethylaminovinyl)]nitrobenzene [34].…”

Section: Resultsmentioning

confidence: 80%

“…[26,31,32]). The former bonds in N,N-dimethyl-p-nitroaniline [33] and in 4-amino-4 0 -nitrobiphenyl [35] are also longer than the latter which proves that the ground-state charge transfer in these compounds takes place. One should realize, however, that evaluation of the contribution of the quinoid resonance structure in such compounds is difficult.…”

Section: Resultsmentioning

confidence: 85%

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Effect of vinylene and 1,4-phenylene spacers on efficiency of the ground-state intramolecular charge-transfer in enlarged 4-dimethylamino-1-methylpyridinium cations

et al. 2009

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15 N NMR chemical shifts of the exo-and endocyclic nitrogen atoms show how efficient is the ground-state intramolecular charge transfer between these sites in 4-dimethylamino-1-methylpyridinium cation (increased contribution of the quinoid resonance form results in a shielding and deshielding effect of their NMR signals, respectively). As it was anticipated, insertion of vinylene and/or 1,4-phenylene spacers to the cation considerably hinders the ground-state charge transfer. This hypothesis is further supported by an analysis of the C-NMe 2 bond lengths (X-ray data show that spacers elongate this bond). The selected valence angles in the compounds studied are also linearly dependent on d( 15 N endo ) and d( 15 N exo ) values. Although the correlation coefficient for the d( 15 N endo ) versus d( 15 N exo ) dependence is equal to 0.983, decrease of the net charge on one nitrogen atom is not compensated entirely by its increase on another nitrogen atom. This shows that exocyclic nitrogen atom is not the only acceptor of the positive charge in the molecule.The natural population analysis shows that the positive charge is transferred not only to the exocyclic N but also to, e.g., 1-and N-methyl C as well as to C3 and C5 atoms in pyridine ring. Ground-state charge transfer through the p-phenylene moiety was found to be less effective than through the trans-vinylene bridge.

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Section: Resultsmentioning

confidence: 80%

Section: Resultsmentioning

confidence: 80%

Section: Resultsmentioning

confidence: 85%

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Effect of vinylene and 1,4-phenylene spacers on efficiency of the ground-state intramolecular charge-transfer in enlarged 4-dimethylamino-1-methylpyridinium cations

et al. 2009

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“…This is best observed by their very pronounced π-conjugated character, as represented by their C1-N1 and C7-N2 bond lengths, which range from 1.337(3)-1.359(2) Å and 1.321(3)-1.342(5) Å, respectively; these values are even shorter than the C-N amine bond lengths in the classically strong D -π-A molecule, p -nitroaniline (1.355 Å) [ 26 ] and in its more chemically comparable N , N -dimethylaniline derivative (1.358 Å). [ 27 ] The D -π-A molecular architecture of 1-4 is therefore described by the donation of electronic charge from the lone pair of N1 into the π-conjugated system which propagates to the positively charged N2, receiving electron density through dative bonding of its lone pair.…”

Section: Defi Ning the D -π-A Molecular Architecture And Ict Charactementioning

confidence: 99%

Transforming Benzophenoxazine Laser Dyes into Chromophores for Dye‐Sensitized Solar Cells: A Molecular Engineering Approach

Schröder

Cole

Waddell

et al. 2015

Advanced Energy Materials

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next-generation environmental technologies for advanced harvesting of solar energy. The operating principles of DSCs are well documented: a photoanode (working electrode) is covered in mesoporous and nanocrystalline metal oxide (usually TiO 2 ), which is sensitized by a monolayer of dye molecules adsorbed via anchoring groups. [ 2 ] Upon photon absorption, the excited dyes inject an electron into the conduction band of the semiconducting TiO 2 , generating a potential difference with respect to this working electrode and a counter-electrode (a transparent conducting oxide, usually fl uorine-doped tin oxide FTO). Thus, the adsorbed electron is transported to the counter-electrode, i.e., initiating the electrical current in the solar cell. An electrolyte solution between these electrodes acts as a redox couple, taking the electron from the counter-electrode and passing it back to the dye in order to regenerate its ground state, thus completing the electrical circuit. The redox process is catalyzed by platinum, a thin fi lm of which is coated into the counter-electrode. Due to its slow recombination with electrons from TiO 2 , the redox couple typically employed is I − / I 3 − . However, it is worth noting that a Co (II/III) tris(bipyridyl) redox couple is gaining traction as an alternative, given that it has a higher redox potential ( E redox ≈ +0.535 V) compared to I − / I 3 − ( E redox ≈ +0.35 V) and it mitigates better against energy losses in the dye regeneration process. [ 1,3,4 ] As the most effi cient, and hence most commonly used dyes contain the expensive and relatively rare transition metal ruthenium, [ 5,6 ] metal-free organic dyes have become attractive candidates due to their low cost, high molar extinction coeffi cients, and inherent design fl exibility. [ 5,6 ] Most organic dyes are based on donor-(π-bridge)-acceptor ( D -π-A ) architectures, in which a π-conjugated system connects an electron-donating group ( D ) with an electron-accepting group ( A ). Upon photoexcitation, the resulting "push-pull" effect is characterized by anisotropic intramolecular charge transfer (ICT) from the donor to the acceptor, which facilitates electron injection into the semiconductor. Modifi cations to the three main components of the D -π-A architecture allow a fi ne-tuning of the magnitude of this "push-pull" effect, in terms of the molar extinction coeffi cient (ε), the maximum peak absorption wavelength (λ max peak ), tris(bipyridyl) suggests promise for these computationally designed dyes as co-sensitizers for DSC applications.

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“…N,N-dimethyl-4-nitroaniline (DMNA) is an effective chromophore and usually is used as a reference chromophore for study of NLO properties of chromophores [33,34]. Therefore, a series of chromophores with two or multiple parallel and non-conjugated DMNA units were designed, and their static first hyperpolarizabilities (β 0 ) were given from quantum chemistry calculations for investigating relationship between static first hyperpolarizabilities of "parallel connection" chromophores and the number of parallel non-conjugated DMNA units in the chromophore (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Effect of the Number of N,N-dimethyl-4-nitroaniline Units in Novel “Parallel Connection” Chromophores on Its Nonlinear Optical Properties

Zhang

Cao

Zhaobing

2012

ISRN Physical Chemistry

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Design of "parallel connection" chromophores could give a way of acquiring effective chromophores. The semiempirical method ZINDO was employed to study relationship between static first hyperpolarizabilities of "parallel connection" chromophores and the number of parallel nonconjugated N,N-dimethyl-4-nitroaniline (DMNA) units in the chromophore. The results show that the chromophore containing three parallel non-conjugated DMNA units exhibits the highest static first hyperpolarizability, which is 1.8 times that of chromophore DMNA. However, static first hyperpolarizabilities of the chromophores containing four or five DMNA units are very small. The absorption maximum wavelength (λ max ) of "parallel connection" chromophores is remarkably shorter (34.9 nm-38.1 nm) than that of 1DMNA. Therefore, the "parallel connection" chromophore containing three DMNA units would be an effective chromophore with a large first hyperpolarizability and a good optical transparency. It could give a useful suggestion for designing effective chromophores containing parallel non-conjugated D-π-A units.

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Experimental and theoretical study of the structure of N,N-dimethyl-4-nitroaniline derivatives as model compounds for non-linear optical organic materials

Cited by 35 publications

References 27 publications

Effect of vinylene and 1,4-phenylene spacers on efficiency of the ground-state intramolecular charge-transfer in enlarged 4-dimethylamino-1-methylpyridinium cations

Effect of vinylene and 1,4-phenylene spacers on efficiency of the ground-state intramolecular charge-transfer in enlarged 4-dimethylamino-1-methylpyridinium cations

Transforming Benzophenoxazine Laser Dyes into Chromophores for Dye‐Sensitized Solar Cells: A Molecular Engineering Approach

Theoretical Study of Effect of the Number of N,N-dimethyl-4-nitroaniline Units in Novel “Parallel Connection” Chromophores on Its Nonlinear Optical Properties

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