Hydrothermal Preparation and Photophysical Properties of a Ni(II) Complex Containing Quinoline Derivative and Phen Ligands①

CHEN Hai-Hui YI Xiu-Guang PAN Chang-Wang WEN Ji-Wu ZHANG Cong

Hydrothermal Preparation and Photophysical Properties of a Ni(II) Complex Containing Quinoline Derivative and Phen Ligands①

CHEN Hai-Hui YI Xiu-Guang②PAN Chang-Wang WEN Ji-Wu ZHANG Cong

(343009)

hydrothermal preparation, crystal structure, photophysical properties;

1 INTRODUCTION

The coordination complexes have a wide application prospect in the fields of fluorescent materials, semiconductor materials, magnetic materials solar cells and biomedicine[1-4].However, in the design process of coordination complexes, the selection of metal ions is relatively limited, while the selection of ligands in infinite.Especially in the aspect of ligands containing nitrogen and oxygen atoms at the same time, nitrogen and oxygen atoms have not only different coordination modes, but also different rigidity and flexibility.

Quinoline carboxylic acid derivatives are very interesting organic ligands.Many quinoline carboxylic acid derivatives possess a variety of biological activities, such as antibacterial activities, anti-inflammatory[5, 6], and so on.Quinoline carboxylic acid derivatives also have luminescent properties based on the special structures of quinoline carboxylic acid derivative ligands.Quinoline carboxylic acid ligands have nitrogen and oxygen atoms at the same time, which can produce a variety of coordination modes, such as single tooth, multi tooth, bridging[7, 8], and so forth.

Base on the special interest in quinoline carboxylic acid derivatives, a series of metal complexes with the ligand were reported by our group[9], such as mononuclear Zn(II)/Ni(II)/Pr(III) complexes with monodentate coordina- tion and mononuclear Cu(II)/Zn(II) complexes with bidentate chelated coordination.In the continuing of our work, we report here the hydrothermal preparation and photophysical properties of a Ni(II) complex, which is a binuclear complex with both bridging and chelating modes.

2 EXPERIMENTAL

2.1 General procedure

All reactants of A.R.grade were commercially obtained and used without further purification.The infrared spectrum was measured on a PE Spectrum-One FT-IR spectro- photometer over the frequency range of 4000～400 cm-1by using the KBr pellet technique.1H NMR spectra were measured on a Bruker Avance 400 MHz instrument with DMSO-d6 as the solvent.The solid state UV/Vis diffuse reflectance spectroscopy was investigated using TU-1901 UV/Vis spectrometer.The photoluminescence of solid state samples was investigated using the FX-97XP fluorescence spectrometer.

2.2 Preparation of quinoline derivative (3-hydroxy-2-methyl-quinoline-4-carboxylic acid)

The synthesis of quinoline derivative was based on relevant references[10, 11], which was briefly introduced as follows: firstly, indigo was oxidized by K2CrO7to form the intermediate product isatin.Secondly, the ligand 3-hydroxy- 2-methyl-quinoline-4-carboxylic acid was obtained by adding chloroacetone to the isatin in alkaline condition.

2.3 Preparation of the title complex

The title complex was prepared by mixing Ni(CH3COO)2·4H2O (2 mmol, 497.4 mg), 3-hydroxy- 2-methyl-quinoline-4-carboxylic acid (2 mmol, 406 mg), phen (3 mmol, 540 mg), Et3N (4 mL) and distilled water (15 mL) mixed in a 25 mL Teflon-lined stainless-steel autoclave.The mixture was heated to 393 K and kept at this temperature for one week.After cooling the mixture slowly down to room temperature, yellowish crystals suitable for X-ray analysis were collected and washed.Yield: 75% (based on nickel).IR (KBr, cm-1): 3432 (vs), 3061 (w), 1634 (w), 1584 (m), 1525 (m), 1476 (m), 1433 (m), 1309 (w), 1222 (m), 1143 (w), 851 (m), 764 (m), 730 (m), 634 (w).

2.4 X-ray structural determination

A carefully selected single crystal of the title complex was collected on a SuperNova CCD X-ray diffractometer equipped with a graphite-monochromated Moradiation (= 0.71073 ?) with anscan method.The reduction and empirical absorption correction of diffraction data were carried out with the SIR2004.Using Olex2[12], the structure of the title complex was solved by ShelXH[13]and refined by ShelXL[14]refinement package with full-matrix least-squares.All of the non-hydrogen atoms were generated based on the subsequent Fourier difference maps and refined anisotropically.The hydrogen atoms, except for the lattice water, were located theoretically and ride on their parent atoms.Reflections measured are 19494; the final= 0.0780 for 699 parameters and 9118 observed reflections with> 2() and= 0.2318, index ranges are –14≤≤14, –14≤≤15, –20≤≤20,= 1.017, (Δ)max= 1.488 and (Δ)min= –1.135 e/?3.The selected bond distances and bond angles are shown in Table 1.

Table 1.Selected Bond Lengths (?) and Bond Angles (°)

3 RESULTS AND DISCUSSION

Table 2.π-π Stacking Interactions of the Title Complex

Fig.1.Molecular structure of the title complex.Hydrogen atoms and lattice water molecules are omitted for clarity

Fig.2.-stacking interaction diagram of the title complex.Hydrogen atoms and three lattice water molecules are omitted for clarity

Based on consideration, increasing attention has been paid to the photoluminescence of coordination complexes.We conducted photoluminescence spectral analysis on solid state sample of the title complex at room temperature and the result is shown in Fig.3.The photoluminescent spectra of the Ni(II) complex display effective energy absorption in the range of 225～350 nm.When the emission is 416 nm, the excitation spectra of the title complex show the band at 286 nm.Further, we measured the corresponding photolumi- nescence emission spectra of the title complex.Upon excitation at 286 nm, the blue purple region of the spectra showed a similar peak of 449 nm.The Commission International De I-‘Eclairage (CIE) 1931 chromaticity coordinates under emission were calculated for the title complex.The estimated CIE values were found to be= 0.1691 and= 0.007, as shown in Fig.4.Therefore, we deem that the title complex is a promising blue purple light emitting diode material.

Fig.3.Solid-state excitation and emission spectra of the title complex.The inset is the solid-state photoluminescence spectra of the title complex

Fig.4.CIE chromaticity diagram and chromaticity coordinates of the emission spectra of the title complex

As the diffuse reflectance spectroscopy (DRS) can be helpful to understand the conductance property of materials, UV-Vis DRS analysis on solid state sample of the title complex was carried out at room temperature on the basis of barium sulfate as a reference giving 100% reflectivity, with the result shown in Fig.5.The Kubelka-Munk function (=/= (1 –)2/2) was used to process the data[17]after measuring the DRS of solid state.The-axis is transformed from the Kubelka-Munk and the-axis is transformed from the energy formulaE=/.For this function, the parameters of,,andstand for the absorption coefficient, the scattering coefficient, the reflection coefficient and the absorption wavelength, respectively.From the plot of/λ vs E, we can obtain the value of the optical band gap, which can be extrapolated from the linear part of the absorption edge.The solid-state UV-Vis DRS shows the band width of the title complex is 1.702 eV.The energy band gap of the title complex is obviously larger than those of GaAs (1.40 eV), CdTe (1.50 eV), and CuInS2(1.55 eV), which are well known as highly efficient band gap photovoltaic materials[18-20].Therefore, we deem that the title complex may represent highly efficient band gap photovoltaic materials.

Fig.5.Solid-state UV-Vis DRS of the title complex.The inset is the UV-Vis spectra of the title complex

4 CONCLUSION

In summary, a nickel compound has been prepared through a hydrothermal reaction and characterized by single-crystal X-ray diffraction.It is characterized by a 1-chain-like structure.Solid-state photoluminescence reveals that the title complex shows blue purple emission.Solid-state DRS revealed the presence of a narrow optical band gap of 1.702 eV, indicating that the title complex is a candidate for narrow optical band gap organic semiconductor material.Further investigations on the relationship between the structure and the properties of nickel crystalline complex are in progress in our laboratory.

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3 August 2020;

24 September 2020 (CCDC 2018168)

①We gratefully acknowledge the financial support of the National Natural Science Foundation (51363009), and Jiangxi Provincial Natural Science Foundation (20202BAB204003), Jiangxi Provincial Department of Education’s Item of Science and Technology (GJJ190550), and Doctoral Research Startup Foundation of Jinggangshan University (JZB1905)

.Yi Xiu-Guang, male, associate professor, majoring in inorganic chemistry.E-mail: jayxgggchem@163.com

10.14102/j.cnki.0254–5861.2011–2951