HF and DFT studies of the structure and vibrational spectra of 8-hydroxyquinoline and its mercury(II) halide complexes

doi:10.1016/j.saa.2004.03.026

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Volume 61, Issues 1–2, 1 January 2005, Pages 37-43

https://doi.org/10.1016/j.saa.2004.03.026 Get rights and content

Abstract

The geometry, frequency and intensity of the vibrational bands of 8-hydroxyquinoline (8-HOQ) were obtained by HF and density functional theory (DFT) with BLYP and B3LYP functionals and 6–31G(d) as the basis set. The optimized bond lengths and bond angles are in good agreement with the X-ray data. The vibrational spectra of 8-HOQ which is calculated by the HF and DFT methods, reproduces the vibrational wavenumbers and intensities with an accuracy, which allows reliable vibrational assignments. Complexes of the type Hg(8-HOQ)X₂ [where X=Cl, Br] have been studied in the 4000–200 cm⁻¹ region, and assignment of all the observed bands were made. The analysis of the infrared spectra indicates that there are some structure-spectra correlations.

Introduction

8-Hydroxyquinoline (8-HOQ) and its derivatives are well known for their antifungal, antibacterial and antiamoebic activities [1]. These molecules are so widely employed as a good fluorogenic ligand binding with many metal cations due to its low quantum yield in aqueous and some organic solutions [2]. After loosing a proton, 8-HOQ and its derivatives are capable of forming complexes with a large number of both main group and transition metal ions [3]. The complexes of magnesium, aluminum, zinc and boron have attracted particular attentions in recent years because of their applications in organic electroluminescence (OEL) devices [4], [5], [6], [7].

The detailed crystal data on metal 8-hydroxyquinolinate dihydrates were reported by Merritt et al. [8], [10] and Palenik [9], [11]. The infrared spectra of some bivalent and tervalent metal chelate compounds of 8-HOQ were reported by Magee and Gordon [12], [13], [14], who gave some vibrational modes of 8-HOQ.

In 1971, Ohkaku and Nakamoto [15] and later Engelter et al. [16] reported the IR spectra of M(8-OQ)₂(H₂O)₂ [M=Mn, Fe, Co, Zn, Ni, Cu], M(8-OQ)₂ [M=Mn, Co, Ni, Cu, Zn] and M(8-OQ)₃ [M=Sc, V, Cr, Mn, Fe, Co, Ga] compounds over the range 700–50 cm⁻¹. There, metal–ligand assignments are also given.

Recently, Cheatum et al.[17] have investigated excited-state dynamics of 8-HOQ dimers, and Li and Fang [18] have carried out a combined CASSCF, density functional theory (DFT) and MP2 study on the ground- and excited-state proton transfer processes of 8-HOQ. But up to now, no ab initio and DFT calculation has been given on 8-HOQ.

In our previous work [19], we reported the IR spectra of M(8-HOQ)₂X₂ [M=Zn, Co; X=Cl, Br, I and M=Fe; X=Cl] complexes.

In this study, we report ab initio HF and DFT/B3LYP, BLYP calculation results on 8-hydroxyquinoline. The aim of this study is to give optimal molecular geometry, vibrational wavenumbers and modes of free 8-HOQ. We have also reported the IR spectra of mercury (II) halide complexes of 8-hydroxyquinoline, to detect any relation between the ligand vibrational values and the metal.

Section snippets

Computational details

All calculations reported here were carried out using the GAUSSIAN 98 package of program [20], and using Gauss-view molecular visualization program [21] on the personal computer.

Experimental

All chemicals were reagent grade and were used without further purification. Mercury chloride and bromide (1 mmol) was dissolved in absolute ethanol (10 ml). To this, 1 mmol of 8-hydroxyquinoline solution in ethanol was added. The mixture was stirred magnetically at room temperature. The precipitated complexes were filtered, washed with ether and dried. The freshly prepared compounds were analyzed for C, H, and N by a Leco CHN-600 Model analyzer with the following results (% found/% calculated). $Hg$

Results and discussion

The molecular structure of 8-HOQ reported earlier [22] was based on photographic data and presented as monomer. Later, it has been refined by Banerjee and Saha [23] with diffractometric data in order to locate the hydrogen atoms and to make more quantitative comparisons with other similar structures. They have shown that two 8-HOQ molecules form a dimer with two inter-molecular O–H⋯N hydrogen bonds.

The molecular structure and numbering of atoms of 8-HOQ is shown in Fig. 1.

Conclusion

The structural parameters, IR frequencies and intensities of the fundamental vibrational bands of 8-HOQ were calculated at the HF and DFT/BLYP, B3LYP methods and 6–31G(d) as the basis set. The infrared absorption and intensities computed by B3LYP method are in reasonable agreement with the experimental data. The results confirm the ability of the methodology applied for interpretation of the vibrational spectrum of the 8-HOQ molecule in the solid state.

The IR spectroscopic study of two new

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HF and DFT studies of the structure and vibrational spectra of 8-hydroxyquinoline and its mercury(II) halide complexes

Abstract

Introduction

Section snippets

Computational details

Experimental

Results and discussion

Conclusion

Talanta

Talanta

Talanta

J. Mol. Struct

Chem. Phys. Lett

Chem. Phys. Lett

Bull. Korean Chem. Soc

Spectrochim. Acta

J. Mol. Spectrosc

Jpn. J. Appl. Phys

Appl. Phys. Lett

J. Am. Chem. Soc

Jpn. J. Appl. Phys