Synthesis, Characterization, and Optical Properties of Organic

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Synthesis, characterization and optical properties of organicinorganic hybrid layered materials: a solvent-free ligand-controlled dimensionality approach based on metal sulfates and aromatic diamines Anabel Gonzalez Guillen, Marcin Oszajca, Katarzyna Luberda-Durna#, Marlena Gryl, Stanis#aw Bartkiewicz, Andrzej Miniewicz, and Wieslaw Lasocha Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00466 • Publication Date (Web): 26 Jun 2018 Downloaded from http://pubs.acs.org on June 26, 2018

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Crystal Growth & Design

Synthesis, characterization and optical properties of organic-inorganic hybrid layered materials: a solvent-free ligand-controlled dimensionality approach based on metal sulfates and aromatic diamines. Anabel González Guillén, Marcin Oszajca, Katarzyna Luberda-Durnaś†, Marlena Gryl, Stanisław Bartkiewicz††, Andrzej Miniewicz††, Wieslaw Lasocha*†††. Faculty of Chemistry, Jagiellonian University, Gronostajowa 2 , 30-387 Krakow. KEYWORDS A. Hybrid materials, B. X-ray diffraction, C. chemical synthesis, D. NLO materials.

ABSTRACT

A new family of organic-inorganic hybrid layered materials based on cadmium and zinc sulfates was synthesized using 1,2-phenylenediamine (OPD), 1,3-phenylenediamine (MPD) and 1,4phenylenediamine (PPD) as organic templates and ligands. The diamines act as structuredirecting agents to obtain 1D, 2D and 3D frameworks. Six new materials were obtained utilizing

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a simple, solvent-free synthesis approach: 1D: (OPD)2ZnSO4 1, (OPD)2CdSO4 2; 2D: (MPD)2ZnSO4 3, (MPD)2CdSO4 4; 3D: (PPD)ZnSO4 5, (PPD)CdSO4 6. The synthesis method has proven to be scalable and robust. The crystal structures were determined using data from Xray powder diffraction measurements (XRPD). It was observed that the type of amine determines the dimensionality of the obtained materials. 1D, 2D and 3D structures were obtained using ortho-, meta- and para-phenylenediamine isomers, respectively. The phase purity of the samples was confirmed by elemental analysis and the morphology of the crystallites was studies using scanning

electron

microscopy

(SEM).

The

thermal

stability

was

determined

by

thermogravimetry (TG) and non-ambient XRPD techniques. Additional characterization was performed for the two non-centrosymmetric, polar materials 3 and 4. Second order nonlinear optical (NLO) properties were examined using both, experimental measurements (Second Harmonic Generation) and theoretical calculations.

Introduction Hybrid organic-inorganic materials have been intensively investigated for at least three decades.[1–5] Nevertheless, new interesting compounds are still being discovered due to a large variety of available organic and inorganic components, as well as emerging synthesis techniques using different experimental conditions.[6–11] It has been shown that hybrid organic-inorganic compounds play a prominent role in the development of new advanced functional materials.[12–15] Due to the complementary properties of the organic (flexibility and structural diversity) and inorganic (rigidity and stability) components, these materials are suitable for many applications in areas such as optoelectronics,[16] environmental protection,[14] or catalysis.[17,18] The structure diversity of hybrid materials gives almost limitless possibilities of obtaining crystals with different properties. However, controlling the magnitude of a particular physical effect often


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requires steering of molecular self-assembly. There is no direct recipe for a successful design of all functional materials; however, we can retain some degree of control through crystal engineering. The literature reports show that temperature,[19] pH value,[20] stoichiometry,[21] and template molecules[22] have a great influence on the reaction outcome. Nevertheless, a ‘single set of factors’ that determines the dimensionality of the resulting framework of a hybrid organicinorganic material has not been identified up to this point. Although many different organic molecule types have been used as templates[23–28] it is well known that amines and diamines are very important building-blocks in the synthesis of hybrid materials.[29–33] Paul et al.[34] and Liu et al.

[35]

present good examples of aromatic amines (specifically, polyazaheterocycles and

triazole derivates) used as organic block and cadmium sulfates as inorganic part where 2D and 3D frameworks were synthesized. The use of different structural isomers as organic buildingblocks was previously studied by Thirumurugan and Rao[36] and Zheng He et al.[37] Thirumurugan and Rao presented a group of hybrid compounds that contain isomers of benzenedicarboxylic acid as organic components in the presence or absence of amines acting as chelating ligands, and Zn or Cd as metal centers. However, due to the presence of linkers, chelating ligands and solvent, the degree of control over the dimensionality of the crystal structures obtained with these isomers is not directly dependent upon the isomer type. Zheng He et al. synthesized a family of coordination polymers presenting a more systematic approach to a dimensionality-controlled method by using pyridine carboxylate N-oxide isomers and Gd(III) salts. To the best of our knowledge, this is the first report of a solvent-free synthesis of hybrid materials engineered with specific dimensionality depending directly on the isomers of the organic component.


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We wanted to focus on a simple, robust, solvent-free synthesis method using just aromatic diamines and a metal sulfate (Cd/Zn). Herein, six new hybrid materials were obtained where the aromatic diamine acts as a structure-directing agent to systematically tune the frameworks´ dimensionality using similar organic building-blocks. Polymeric 1D chains, 2D layers, and 3D structures were obtained when ortho-, meta-, or para-phenylenediamines were used, respectively. In our previous research[32] meta- and para-xylylenediamine materials with Zn and Cd sulfates were investigated. It was observed that meta-xylylenediamine has a tendency to crystallize in non-centrosymmetric space groups. Because of this, it was also interesting to confirm a correlation between the lack of inversion center and the meta isomer. In fact, we have obtained two new polar materials using the meta isomer and tested them in the context of non-linear optical properties (NLO). We have examined second harmonic generation (SHG), for the powdered samples 3 and 4, which is a known second-order NLO effect. It is well known that only materials without an inversion center can exhibit nonlinear optical properties of even orders.[38] Thus, the observation of SGH signal from a powdered sample provided additional proof of non-centrosymmetricity of the examined crystals.

Experimental Section ZnSO4·7H2O and CdSO4·8/3H2O (Avantor Performance Materials Poland S.A.), ophenylenediamine (C8H12N2), p-phenylenediamine (C8H12N2), and m-phenylenediamine (C8H12N2) (99%, Sigma-Aldrich) were used as received without further purification. All materials were synthesized by heating the reagents in a Teflon-lined stainless steel autoclave. No solvent or excess of any reactant was used. The final products crystallized as fine powders. (OPD)2ZnSO4 1, (OPD)2CdSO4 2, (MPD)2ZnSO4 3 and (MPD)2CdSO4 4. 20 mmol


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(2.16 g) of the corresponding amine (MPD or OPD) and 10 mmol of the metal sulfate, (1.79 g) ZnSO4·H2O for 1 and 3; or 10 mmol (2.56 g) of CdSO4·8/3H2O for 2 and 4; were weighed and transferred to a 60-ml sealed Teflon-lined stainless steel autoclave. The reactants were heated at 120°C for 3 days and left to cool down to room temperature. Afterward, the products were washed with propanol (x2) and left to dry at room temperature for 12 h to obtain the final powder products. Elemental analysis calculated (%) for ZnSO4C12H16N4 1: (377.7 g·mol–1): C, 38.15; H, 4.27; N, 14.83. Found C, 38.04; H, 4.43; N 14.61. Yield: ca. 94%. Elemental analysis. Calculated (%) for CdSO4C12H16N4 2: (424.8 g·mol–1): C, 33.93; H, 3.80; N, 13.19. Found C, 34.16; H, 3.43; N, 13.50. Yield: ca. 89.2%. Elemental analysis calculated (%) for 3 ZnSO4C12H16N4 (377.3 g·mol–1): C, 38.15; H, 4.27; N, 14.83. Found C, 37.90; H, 4.12; N, 14.59 Yield: ca. 92.7%. Elemental analysis calculated (%) for CdSO4C12H16N44 (424.8 g·mol–1): C, 33.93; H, 3.80; N, 13.19. Found C, 33.74; H 3.67; N, 12.86. Yield: ca. 93.1%. (PPD)ZnSO4 5 and (PPD)CdSO4 6. 10 mmol (1.08 g) of 1,4-phenylenediamine and 10 mmol (1.08 g) of ZnSO4·H2O for 5; or 10 mmol (2.56 g) of 8CdSO4·3H2O for 6; were weighed and transferred to a 60-ml sealed Teflonlined stainless steel autoclave, heated at 120°C for 3 days, and left to cool down to room temperature. The products were washed with a mixture of water and propanol 1:1 (x2) and left to dry at room temperature for 12 h to obtain a final powder product. Elemental analysis calculated (%) for ZnSO4C6H8N2 5 (269.6 g·mol–1): C, 26.74; H, 2.99; N, 10.39. Found C, 27.3; H, 3.34; N, 10.70. Yield: ca. 93.3%. Elemental analysis calculated (%) for CdSO4C6H8N2 6 (316.6 g·mol–1): C, 22.76; H, 2.54; N, 8.85. Found C, 22.64; H, 2.55; N, 8.81 Yield: ca. 92.8%. Additionally, the synthesis of all materials was performed several times proving the robustness of the method as well as its scalability in the ‘laboratory scale range’ (scaled up to 6 times). The crystallographic data for the compounds 1−6 were deposited with the Cambridge Crystallographic Data Center


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(CCDC). The CCDC numbers for the compounds are 1 – 1521451, 2 – 1521452, 3 – 1521455, 4 – 1521450, 5 – 1521454 and 6 – 1521453. X-ray investigation: X-ray powder diffraction measurements (XRPD) were performed with an X’Pert PRO MPD diffractometer working in Bragg-Brentano geometry: incident and antiscatter slits of 1/4 and 1/2°; X-ray source: LFF tube, copper anode CuKα (1.54178 Å); operating power: 40 kV and 30 mA. The diffraction patterns were recorded at room temperature in the range 4– 90° 2θ; interpolated step size: 0.02°; detector: PIXCEL. Non-linear optical activity: SHG experiments were done using SURELITE II Nd:YAG pulsed laser with removed SHG and THG units for obtaining pure infrared beam. Elemental analyses were performed with a Euro Vector EA 3000 Elemental Analyzer. Thermal analysis: Thermogravimetric (TG) analyses of the materials were completed on a TA Discovery thermal analyzer by TA Instruments (Waltham, Massachusetts, USA), with an absolute weighing error of

Synthesis, Characterization, and Optical Properties of Organic

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