Effect of structural changes in sesquifulvalene on the intramolecular charge transfer and nonlinear polarizations – a theoretical study

Nandi, Prasanta K.; Mandal, K.; Kar, Tapas

doi:10.1016/j.cplett.2003.09.135

Cited by 33 publications

(16 citation statements)

References 24 publications

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“…14 It would be worthwhile to mention the extent of charge transfer that is expected to provide stronger H-bonding interaction between the acceptor group and the H-atom of the donor ring. 9 The calculated first hyperpolarizability (ˇt ot ) and the groundstate dipole moment ( g ) are 7.20295 ð 10 31 e.s.u. and 11.786 Debye, respectively.…”

Section: Effect Of Ionic Hydrogen Bonds and Planarity On Nlo Propertiesmentioning

confidence: 99%

“…Presently, intramolecular charge-transfer (ICT) chromophores have received overwhelming attention in the search for materials with high non-linear responses. 9 Chirality 10 and hydrogen bonding 11 are important factors in the design of NLO chromophores since the measurement of bulk NLO properties in the solid state (necessary for device manufacture) is dependent on a non-centrosymmetric packing environment within the crystal lattice. Several groups have reported the introduction of chirality into the chromophores using L-proline as a donor residue.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Vibrational spectral studies and the non‐linear optical properties of a novel NLO material L‐prolinium tartrate

Padmaja¹,

Vijayakumar²,

Joe³

et al. 2006

J Raman Spectroscopy

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Vibrational spectral analysis of the novel non-linear optical (NLO) material, L-prolinium tartrate (LPT) was carried out using NIR-FT-Raman and FT-IR spectroscopy. The density functional theoretical (DFT) computations have been performed at B3LYP/6-31G (d) level to derive equilibrium geometry, vibrational wavenumbers, intensities and first hyperpolarizability. The reasonable NLO efficiency, predicted for the first time in this novel compound, has been confirmed by Kurtz-Perry powder second-harmonic generation (SHG) experiments. The charge-transfer interaction between the pyrrolidine ring and the carbonyl group of the tartrate anion through the intramolecular ionic hydrogen bonds is confirmed by the simultaneous activation of ring modes in IR and Raman spectra. The splitting of the ring-breathing mode, pseudorotational ring puckering modes and the NH 2 modes of the pyrrolidine ring lead to the conclusion that the pyrrolidine ring adopts a conformation intermediate between the envelope (bent) form and the half-chair (twisted) form, resulting in the lowering of symmetry fromC 2 to C s . The lowering of the methylenic stretching wavenumbers and the enhancement of the stretching intensities suggest the existence of the electronic effects of back-donation in LPT. The positional disorder of the pyrrolidine ring, the presence of blue-shifting H-bonds as well as other non-bonded interactions in LPT, low frequency H-bond vibrations and the role of intramolecular charge transfer and the hydrogen bonds in making the molecule NLO active have been analysed on the basis of the vibrational spectral features.

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Section: Effect Of Ionic Hydrogen Bonds and Planarity On Nlo Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Vibrational spectral studies and the non‐linear optical properties of a novel NLO material L‐prolinium tartrate

Padmaja¹,

Vijayakumar²,

Joe³

et al. 2006

J Raman Spectroscopy

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“…The incorporation of heteroatoms into the molecular framework and their position influence the NLO properties. [129] Finally, compound 6 has been described as a chemical chameleon. Ottosson and his group [103] have provided a sound theoretical basis for fulvenes in their T 1 state to be polarised in the opposite direction to S 0 .…”

Section: Pentaheptafulvalenes (Sesquifulvalenes)mentioning

confidence: 99%

The Fulvalenes

Halton

2005

Eur J Org Chem

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The fulvalenes are the class of hydrocarbons obtained by formally cross‐conjugating two rings through a common exocyclic double bond. Although the first report of such a compound dates to 1915, study of the series began in earnest only in the 1950s, and even today many of the unsubstituted parent hydrocarbons remain unknown. The following report, the first to specifically address this class of molecules, summarises the information available from research published to the end of 2004 and offers some suggestions for future study. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…[81] It would be worthwhile to mention that the extent of charge transfer is expected to provide stronger H-bonding interaction between the acceptor group and the H atom of the donor group. [82] The profound influences of hydrogen bonding on crystal structure are clear, but the significance of the presence of these bonds on the hyperpolarizabilities of this molecule is not presently well understood and work is in progress with the help of both computations and spectroscopy.…”

Section: Effect Of Ionic Hydrogen Bonds On Nlo Propertiesmentioning

confidence: 99%

Vibrational spectral studies on charge transfer and ionic hydrogen‐bonding interactions of nonlinear optical material L‐arginine nitrate hemihydrate

Vijayakumar¹,

Joe²,

Nair

et al. 2008

J Raman Spectroscopy

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The near infrared Fourier-transform (NIR FT)-Raman and Fourier-transform infrared (FT-IR) spectroscopies supported by HF/6-31G(d) computations have been employed to derive equilibrium geometry, vibrational wavenumbers and the first hyperpolarizability of the nonlinear optical (NLO) material, L-arginine nitrate (LAN) hemihydrate. The reasonable NLO efficiency, predicted for the first time in this novel compound, has been confirmed by Kurtz-Perry powder second harmonic generation (SHG) experiments. The changes in the atomic charge distribution among different groups due to the presence of strong electronegative atoms and the shrinking of N-O bonds of nitrate anion and C-N bonds of guanidyl group have been analyzed. The splitting of the carboxylate stretching modes, blue shifting of methine vibrations and the electronic effects such as backdonation and induction on the methylene hydrogen atoms have also been examined in detail. The intense low wavenumber H-bond Raman vibrations due to electron-phonon coupling and nonbonded interactions in making the LAN molecule NLO active have been discussed based on the vibrational spectral features. The natural bond orbital (NBO) analysis and HF computations confirm the occurrence of strong intra-and intermolecular N-H· · ·O and O-H· · ·Oionic hydrogen bonding between charged species providing the noncentrosymmetric structure in the LAN crystal.

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Effect of structural changes in sesquifulvalene on the intramolecular charge transfer and nonlinear polarizations – a theoretical study

Cited by 33 publications

References 24 publications

Vibrational spectral studies and the non‐linear optical properties of a novel NLO material L‐prolinium tartrate

Vibrational spectral studies and the non‐linear optical properties of a novel NLO material L‐prolinium tartrate

The Fulvalenes

Vibrational spectral studies on charge transfer and ionic hydrogen‐bonding interactions of nonlinear optical material L‐arginine nitrate hemihydrate

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