Mono BN-substituted analogues of naphthalene: a theoretical analysis of the effect of BN position on stability, aromaticity and frontier orbital energies (original) (raw)
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BN-naphthalene and carbon-containing derivatives: an ab initio study
Journal of Molecular Structure: THEOCHEM, 1997
Ab initio calculations are used to examine the stability of various isomers of benzene and naphthalene after substitution of pairs of carbon atoms by the isoelectronic boron-nitrogen (BN) tandem. It is found that stability is enhanced by keeping the B and N atoms adjacent to one another. When multiple pairs of BN are present, these pairs prefer to be consecutive with one another. The energy is also lowered by maintaining the heteroatoms on the same ring of naphthalene. Another factor is the preference that consecutive carbon atoms be grouped into even numbers. Successively higher degrees of substitution lead to a regular drop in the molecular valency, as well as increased hardness. 0 1997 Elsevier Science B.V.
Russian Journal of Physical Chemistry A, 2014
In this paper, the stabilities and hydrogen bond interactions of 4 chloro 1 naphthol, 1 hydrox ynaphthalene and 1,4 dihydroxynaphthalene dimers have been theoretically investigated by means of study on binding energies with nonlocal hybrid three parameter Lee-Yang-Parr, B3LYP, and M06 class func tional calculations. Calculations on dimers aim to provide as a test of the efficacy of M06 calculations for intermolecular interaction calculations and more strongly bound systems. For hydroxyl and halo substi tuted derivatives of naphthalene, total electronic energies, their correction for the zero point vibrational ener gies with some calculated thermodynamic properties and their relative differences are together in order to dis cuss the rotamer structures. Static (hyper) polarizabilities and the electric dipole moments, frontier molecu lar orbital energy gaps and the relationships between them have been interpreted. Generally, they are seen that the calculated geometric parameters and spectral results were in a good agreement with the corresponding experimental data.
Journal of Molecular Structure: …, 2001
The ground state molecular structure of different single-atom peri-bridged naphthalene compounds containing a fourmembered ring was studied by ab initio quantum chemistry and by density functional theory (DFT) using the Becke, Lee, Yang and Parr density functional method (B3LYP). Also, in some of these compounds, pyramidal atom inversion energy and its transition state structure along with the energetic stability of the favored intermediate in the electrophilic substitution, have been determined using these computational methods. q
Molecular and electronic structure of 1, 8-peribridged naphthalenes
The Journal of Physical …, 2007
The crystal and molecular structure of 1, 8-thianaphthalene has been determined and compared with other single-atom peribridged naphthalenes (SAPN). The measured CSC angle is 73.06°, which is the smallest bridging angle yet recorded for a SAPN derivative. ...
Electronic transition moments in the spectra of substituted naphthalenes
Journal of Crystal and Molecular Structure, 1981
The absorption spectrum of naphthalene is drastically perturbed as a result of substitution, and the perturbation depends on the nature and position of the substituents (Baba and Suzuki, 1961; Suzuki et al., 1973). In the present communication we report the effect of substitution on the orientation of electronic transition moments in naphthalene. The most reliable experimental method of determining this parameter is based on the rotational contour analysis of the electronic-origin band in the absorption spectrum of molecular vapor recorded under high resolution. This has been done for the near ultraviolet spectra of naphthalene and several of its monoderivatives (Hollas and Thakur, 1973, 1974; Singh and Thakur, 1978). The orientation of the electronic transition moment determined by this method is, however, not unambiguous and one has to choose between the two orientations on the basis of molecular-orbital calculations. The choice of the angle between the transition moment vector and the long in-plane axis of the naphthalene ring in the case of 2-hydroxynaphthalene (Hollas and Thakur, 1973) was made on the basis of the MO calculations of Nishimoto (1967). The orientation angle rejected on this basis is, however, found to be in good agreement with a later MO calculation of Suzuki et al. (1973). This ambiguity between the two different sets of calculations is resolved if we remember that the transition moment is represented by a double-headed arrow and that the MO calculations give either the acute or the obtuse angle between this arrow
Effect of hydroxy substituents on the electronic spectra of naphthalene
Acta Physica Hungarica, 1991
The electronic spectra of naphthalene, 1-naphthol, 2-naphthol and 1.2-dihydroxynaphthalene are measured in ethanol and boric acid at room temperature. The changes in positions and intensities of the electronic bands on substituting hydroxy (−OH) groups in the different positions are discussed in terms of the charge transfer character of −OH group and dipole moment of the molecule. This provides information about
Effects of Alkyl Substituents on the Excited States of Naphthalene: Semiempirical Study
The Journal of Physical Chemistry A, 2000
The effects of the successive addition of alkyl substituents (methyl and reduced rings) on the excited states of naphthalene are reported. The calculated electronic states of all the reduced derivatives with two, three, and four substituents are compared with the excited states of their methylated analogues. The excited states of several reduced derivatives with seven and eight substituents are also studied. The AM1 method was used to optimize the geometry of 57 naphthalene derivatives, and excited states were calculated with the ZINDO/S (INDO/S) method. ZINDO/S calculations on naphthalene gave excited states in better agreement with experimental results than with results of other semiempirical (CNDO/S and CNDOL) and ab initio (CIS, TD-HF, and TD-DFT) methods. Successive alkyl substitutions are accompanied by bathochromic displacements of the UV-visible bands, since the occupied orbitals are raised in energy more than the unoccupied orbitals. However, not all available substituent positions in naphthalene alter its orbital energy distribution in the same way when they are occupied by alkyl substituents. Distortion from planarity of the naphthalene skeleton of some reduced derivatives is the cause of "anomalous" bathochromic displacements of the absorption bands.
Journal of the American Chemical Society, 2017
Supporting Information. Experimental procedures, spectroscopic data, additional computational details, complete reference for Gaussian 09, and crystallographic information. This material is available free of charge via the Internet at http://pubs.acs.org. Experimental, computational, and crystallographic information (PDF) BN-9,1-Naph crystal structure (CIF) 7F-BN-9,1-Naph crystal structure (CIF) AUTHOR INFORMATION Ω Z.L. and J.S.A.I contributed equally.
The spectra of 1-bromo-4-methylnaphthalene have been analyzed in the region 4000–400 and 4000–100 cm−1for FTIR and FT-Raman respectively. The optimized geometry, fundamental vibrational frequency and intensity of the vibrational bands of title compound were evaluated using ab initio HF and density functional theory (DFT) levels of theory 6-311G basis set. The Calculated harmonic vibrational frequencies were scaled and the values have been compared with experimental FTIR and FT-Raman spectra. The observed and the calculated frequencies were found to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed spectrograms. Mullikan atomic charge were calculated and interpreted. A study on the electronic properties, such as HOMO and LUMO energies were performed by time independent DFT approach. In addition, molecular electrostatic potential (MEP) and thermodynamic properties were performed. The 1H and 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by gauge independent atomic orbital (GIAO) method and compared with experimental chemical shift of closely related molecules. First order hyperpolarizability and polarizability of title compound were calculated using HF theory. Thermodynamic calculations of title compound were also performed with different temperature.