Elsevier

Journal of Molecular Structure

Volume 1167, 5 September 2018, Pages 134-141
Journal of Molecular Structure

Synthesis and characterization of a prominent NLO active MOF of lead with 1,5-naphthalenedisulfonic acid

https://doi.org/10.1016/j.molstruc.2018.04.068Get rights and content

Highlights

  • A new Pb-MOF has been prepared by single gel diffusion technique at ambient condition.

  • Pb2S2O4 rings in the crystal structure form 1D channel.

  • SHG efficiency of the Pb-MOF is 30 times higher than KDP.

  • The compound exhibits excellent fluorescent properties.

Abstract

A new metal-organic framework of lead, [Pb(1,5-nds)(H2O)3]n (1,5-nds = 1,5-naphthalenedisulfonate) having prominent nonlinear optical property has been prepared by single gel diffusion technique at ambient condition using sodium metasilicate. The second harmonic generation efficiency was analyzed using Kurtz and Perry powder method and was found to be 30 times as large as potassium dihydrogen phosphate (KDP). Single crystal X-ray diffraction studies reveal the crystal structure. The grown crystals were further characterized by elemental analysis, powder XRD study, thermogravimetry, FT-IR and UV–visible spectral studies. The Pb2S2O4 rings in the crystal structure form a 1D channel. Hydrogen bonding and π-π interactions provide additional stability to the compound. Photoluminescence studies were also carried out.

Graphical abstract

A novel MOF of lead, [Pb(1,5-nds)(H2O)3]n (1,5-nds = 1,5-naphthalenedisulfonate) having prominent nonlinear optical property has been prepared by single gel diffusion technique at ambient condition using sodium metasilicate. The most prominent feature of the crystal structure is the presence of Pb2S2O4 rings which form a 1D channel. The compound is further characterized by elemental analysis, FT–IR, powder XRD, UV–Visible and thermogravimetric analysis. Photoluminescence study of the compound has also been carried out.

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Introduction

Metal-organic frameworks (MOFs) are three dimensional network structures of coordination compounds which find many applications in catalysis, ion exchange, gas storage and separation, molecular recognition and so on [[1], [2], [3], [4], [5], [6], [7], [8]]. Synthesis of MOFs involves the combination of two units-metal and organic ligand. Depending on the nature of metal and organic ligand, variety of MOFs can be synthesized. The d and f-block metals are mainly used for the construction of MOFs [9,10]. The s and p-block metals did not get much attention as coordination centers in MOFs [11]. Lead is one of the cheapest metals among the p-block which can show high coordination number up to 12, but it is less exploited [12]. Second harmonic generation (SHG) from MOFs has attracted great attention due to their higher chemical stability and efficient nonlinearities [[13], [14], [15], [16]]. The second harmonic generation is exhibited by non-centrosymmetric crystals due to non-zero hyperpolarizability. However, the literature review shows that some of the centrosymmetric crystals also exhibit SHG. Coordination polymers such as [Zn2(benzoate)4(An2py)2] (An2py = trans,trans-9,10-bis(4-pyridylethenyl)anthracene) [17], [Zn2(benzoate)4(4spy)2] (4spy = 4-styrylpyridine) [18] and strontium cyanurate [19], a Ni(II) complex, hexakis(thiourea)nickel(II) nitrate [20] and organic molecular complexes such as picolinium maleate [21] and caffeinium picrate [22] exhibit SHG even though they belong to the centrosymmetric space group.

Carboxylic acids are one of the most important and widely used organic ligands for the construction of MOFs. However, aromatic sulfonic acids are recently used as organic ligands for the syntheses of MOFs due to their various bonding modes such as monodentate, bidentate, tridentate, bridging bidentate, bridging tridentate, etc. Recently, more attention has been paid for the construction of these metal-sulfonate frameworks owing to their enhanced applications as surfactants, dyes, fuels, lubricants, detergents, anti-oxidants, potential catalysts and non-linear optical materials in comparison with their parent sulfonate complex [[23], [24], [25], [26]]. Aromatic disulfonic acids are relatively less studied even though it has the above mentioned applications. 1,5-Naphthalenedisulfonic acid is one of the less exploited aromatic disulfonic acids for the construction of metal-sulfonate frameworks. However, three dimensional networks are reported in the Li(I), Na(I), K(I), Sr(II) and Ba(II) 1,5-nds and two dimensional networks are found in the Ca(II), Mg(II) and Cd(II) 1,5-nds [[27], [28], [29]]. The six possible coordination modes of 1,5-naphthalenedisulfonate anion with a metal ‘M’ is depicted in Scheme 1.

Herein we report a new metal-organic framework of lead, [Pb(1,5-nds)(H2O)3]n by single gel diffusion technique. To the best of our knowledge, this is the first report of the title compound. Single crystal X-ray diffraction studies reveal the crystal structure. The grown crystals were further characterized by elemental analysis, thermal analysis, FT-IR and UV–visible spectral studies. NLO and photoluminescence properties have been investigated.

Section snippets

Crystal growth of [Pb(1,5-nds)(H2O)3]n

Single gel diffusion technique was adopted for the crystallization of [Pb(1,5-nds)(H2O)3]n [30]. Sodium metasilicate (SMS) was used for the preparation of gel. Good quality crystals are generally obtained by gel method due to the controlled nucleation and convection less growth. SMS is dissolved in double distilled water and the density of solution was found using hydrometer. The crystallization apparatus consists of borosilicate glass tube of length 15 cm and diameter 1 cm. The gel solution

Crystal growth

Good quality single crystals free of inclusions appeared at gel interface after a week. The optimum conditions for crystal growth are pH = 6.0, concentration of 1,5-nds = 0.20 M, concentration of lead nitrate = 0.20 M and gel density = 1.04 gcm−3. The crystals were separated after a growth period of two weeks and it is then washed with water and dried. The photograph of a gel grown crystal is shown in Fig. 1.

Elemental analysis

The percentage of carbon, hydrogen and sulfur present in the compound were

Conclusion

A novel metal-organic framework of Pb(II) with 1,5-naphthalenedisulfonic acid, [Pb(1,5-nds)(H2O)3]n having prominent nonlinear optical property has been prepared by single gel diffusion technique. The SHG efficiency of the title compound is found to be 30 times as large as KDP. The single crystal XRD studies reveal that the crystal consists of Pb2S2O4 rings in the most stable boat-chair conformation and possess 1D channels. The crystals were further characterized by powder XRD, FT-IR,

Acknowledgement

One of the authors S. Shibu Prasad acknowledges the University Grants Commission, Government of India for financial assistance under Faculty Development Programme (FDP). The authors are thankful to the STIC, Cochin University of Science and Technology, India, IISc Bengaluru, India and Govt. College for Women, Thiruvananthapuram, India for analytical facilities. We are thankful to Dr. P.K. Sudhadevi Antharjanam, SAIF, Indian Institute of Technology, Madras, India for providing single crystal

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