Synthesis and DFT calculation of a novel 5,17-di(2-antracenylazo)-25,27-di(ethoxycarbonylmethoxy)-26,28-dihydroxycalix[4]arene

https://doi.org/10.1016/j.saa.2014.09.074Get rights and content

Highlights

  • 5,17-Di(2-antracenylazo)-25,27-di(ethoxycarbonylmethoxy)-26,28-dihydroxycalix[4]arene molecule is synthesized.

  • The title molecule is characterized by FT-IR, 1H NMR and 13C NMR spectra.

  • The vibrational frequencies, chemical shifts and electronic absorption wavelengths are calculated by DFT.

  • Density of the state diagrams and HOMO, LUMO energy gap for the title molecule are analyzed.

Abstract

In this study, 5,17-di(2-antracenylazo)-25,27-di(ethoxycarbonylmethoxy)-26,28-dihydroxycalix[4]arene has been synthesized from 2-aminoantracene and 25,27-dihydroxy-26,28-diethylacetate calix[4]arene. In order to identify the molecular structure and vibrational features of the prepared azocalix[4]arene, FT-IR and 1H NMR spectral data have been used. FT-IR spectrum of the studied molecule is recorded in the region 4000–400 cm−1. 1H NMR spectrum is recorded for 0.1–0.2 M solutions in DMSO-d6 solution. The molecular geometry, infrared spectrum are calculated by the density functional method employing B3LYP level with different basis sets, including 6-31G(d) and LanL2DZ. The chemical shifts calculation for 1H NMR of the title molecule is calculated by using by Gauge-Invariant Atomic Orbital method by utilizing the same basis sets. The total density of state, the partial density of state and the overlap population density of state diagram analysis are done via GaussSum 3.0 program. Frontier molecular orbital (HOMO–LUMO) and molecular electrostatic potential surface on the title molecule are carried out for various intramolecular interactions that are responsible for the stabilization of the molecule. The experimental results and theoretical calculations have been compared, and they are found to be in good agreement.

Introduction

Calix[n]arenes are macrocycles prepared by the base-catalyzed condensation of p-tert-butyl phenol with formaldehyde [1]. The cup-shaped macrocycles possess a hydrophobic cavity capable of binding organic molecules. Calixarenes belong to the important category of building blocks for supramolecular assemblies [2] and molecular recognition, and are widely used as receptors for cations [3], [4], anions [5] and also neutral compounds [6]. However, there are fewer examples of complexation in solution [3] and/or in interfaces [4]. The binding properties of calix[n]arenes and their solubility in organic or aqueous solutions can be tailored by modification of the upper rim (p-position) and lower rim (hydroxyl).

The identification of the structure of the calix[n]arenes has provided further facilities to their applications in different areas. The theoretical studies of the calix[n]arenes have given important information about the physical and chemical properties of them. Functionalized calix[n]arenes have received wide attention for a variety of applications such as recovery of uranium, accelerators for instant adhesives, ionophoric electronic devices, and phase transfer agents [5], [6], [7]. Chemical modification of the upper or lower rim with alkyl groups affords amphiphilic calix[n]arenes [8].

Atalay and et al. [9] have carried out to calculate optimal molecular geometry, vibrational wavenumbers and modes of the free ethene-1,1,2,2-tetrayltetramethylene tetrathiocyanate. Optimized geometrical parameters and vibrational frequencies of this compound by means of HF and B3LYP with the 6-31G(d) basis set have been calculated [9]. Structure and conformational equilibrium of amino and mercaptocalix[4]arenes are studied by Suwattanamala et al. [10]. Previously, density functional theory (DFT) calculations of the electronic structure and bonding in meso-tetraphenylmetalloporphyrins have been carried out [11]. Johansson and et al. [12], [13] studied the spin distribution in low-spin iron porphyrins and compared DFT results with coupled cluster calculations for molecular spin-polarization and charge delocalization in iron porphyrins.

In recent reports [14], [15], [16], [17], we have described the synthesis of new azocalix[n]arenes. By selective p-substitution on the upper rim of calix[n]arene, azocalix[n]arene (n = 4,6) derivatives are isolated and characterized in order to study their enol-keto tautomerization in solution and their absorption properties. In order to extend the calixarene complexing reaction to Fe3+, we have concentrated on complexation between calix[n]arenes (n = 4,6,8) and Fe3+ in order to understand the important properties of calix[n]arene-Fe3+ complexes [18].

In the present study, we have reported the synthesis, characterization and molecular structure of the title molecule. We have attempted to understand the 25,27-dihydroxy-26,28-diethylacetate-5,11-di(2-antracenylazo)calix[4]arene. Theoretically calculated NMR parameters are shown to be very helpful in distinguishing between two (or more) related forms of the same compound, e.g. isomers and tautomers. The aim of this study is that the results obtained on the reaction of azocalix[4]arene with 2-aminoantracene and 25,27-dihydroxy-26,28-diethylacetatecalix[4]arene are analyzed. Therefore, the molecular geometry, vibrational wavenumbers and chemical shifts in the ground state have been calculated via the DFT method.

The rest of the paper is organized as follows; experimental details and some results are presented in the Section of Experimental method. The computational detail is given in the Section of Computational method. The experimental and simulation results for structural, electronic features, chemical shifts and vibrational properties for the title molecule considered in this study are presented and discussed in the Section of Results and discussion. We have also compared the simulation results with the observed data in the same Section. Finally, the summary of our main results are given in the last section.

Section snippets

Generals

All solvents and compounds are commercially graded reagents and they have been used without further purification. Melting points are measured using an Electrothermal IA9100 digital melting point apparatus in capillaries sealed asunder nitrogen and are uncorrected.

Spectra

1H NMR spectrum is recorded for 0.1–0.2 M solutions in DMSO-d6 solution at 303 K with a Bruker AVANCE DRX 500 FT-NMR spectrometer equipped with an inverse detection 5-mm diameter broad-band probe head and z-gradient accessory working at

Computational methods

In recent years, as a result of major advances in theoretical work, ab initio and DFT methods have became significantly. In particular, the elucidation of the structure of organic molecules, DFT methods according to HF methods give highly accurate results [22], [23], [24], [25], [26]. Therefore, DFT methods are preferred in this work. In this study, DFT/B3LYP (Becke’s three-parameter hybrid model using the Lee–Yang–Parr correlation functional) level [27], [28] with using 6-31G(d) and LanL2DZ

Structural analysis

The optimized molecular structure is performed at B3LYP/6-31G(d) and LanL2DZ basis sets. The studied molecule with atom numbering is shown in Fig. 1(a) and (b). The optimized molecular structure that is corresponding to the ground state belongs to C1 point group symmetry. The calculated molecular structure is non-planar. As a result of the theoretical study, molecular structure has been determined that two hydrogen bonds are formed between the O(35)single bondH(36)O(40) atoms and O(38)single bondH(39)H(37) atoms.

Conclusions

In this paper, the title molecule is synthesized and characterized by FT-IR and 1H NMR spectroscopic techniques. Additionally, DFT calculations for the title molecule are presented for the first time. Theoretical calculations are used for the characterization of the title molecule. All theoretical calculations are performed with DFT/B3LYP level, 6-31G(d) and LanL2DZ basis sets. The complete molecular structural parameters of the optimized geometry of the title molecule have been obtained from

Acknowledgement

This study has been supported by Pamukkale University (Grant Nos: 2012FBE002, 2012FBE050, 2013FBE009, 2013FBE013).

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