Synthesis and SHG properties of the melamine-based material (C <sub>3</sub> N <sub>6</sub> H <sub>7</sub> )ZnX <sub>3</sub> (C <sub>3</sub> N <sub>6</sub> H <sub>6</sub> ) (X = Cl, Br)

The zinc halide-melamine system was investigated by conducting exploratory solid-state reactions and hydrothermal syntheses, yielding Zn<sub>3</sub>(OH)<sub>2</sub>Cl<sub>4</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>)<sub>3</sub> and (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnX<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>) with X = Cl and Br. All compounds were characterized by single-crystal X-ray diffraction, revealing that there are two modifications of the melaminium-zinc-chloride-melamine compound, crystallizing with non-centrosymmetric space groups (<i>Pna</i>2<sub>1</sub> and <i>P</i>2<sub>1</sub>). The presence of delocalized π-electron systems in compounds containing cyclic (B<sub>3</sub>O<sub>6</sub>)<sup>3-</sup>, (C<sub>3</sub>N<sub>3</sub>O<sub>3</sub>)<sup>3-</sup>, or melamine derivatives is known to give rise to significant second harmonic generation (SHG) properties, provided that the given structure has no inversion center. All crystal structures feature Zn<sup>2+</sup> in a tetrahedral coordination environment, forming layered structures. Spectroscopic measurements on phase-pure orthorhombic (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnBr<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>) resulted in direct and indirect band gaps of 4.74 eV and 4.46 eV respectively. Measurements of the nonlinear optical response performed on single crystals of three different compounds revealed significant intensities following the sequence monoclinic (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnCl<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>) > orthorhombic (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnBr<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>) > orthorhombic (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnCl<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>). Their SHG properties are compared with those of KTP, one of the most widely used SHG materials.

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Publication Details

Journal
Dalton Transactions
Published
2025-01-01
DOI
https://doi.org/10.1039/d5dt02245b
Primary Topic
Nonlinear Optical Materials Research
Type
article
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article

Synthesis and SHG properties of the melamine-based material (C 3 N 6 H 7 )ZnX 3 (C 3 N 6 H 6 ) (X = Cl, Br)

Hans‐Jürgen Meyer, Patrick Schmidt, Dai Zhang
Dalton Transactions
Nonlinear Optical Materials Research
article

Synthesis and SHG properties of the melamine-based material (C 3 N 6 H 7 )ZnX 3 (C 3 N 6 H 6 ) (X = Cl, Br)

Hans‐Jürgen Meyer, Patrick Schmidt, Dai Zhang
article en

Abstract

The zinc halide-melamine system was investigated by conducting exploratory solid-state reactions and hydrothermal syntheses, yielding Zn<sub>3</sub>(OH)<sub>2</sub>Cl<sub>4</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>)<sub>3</sub> and (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnX<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>) with X = Cl and Br. All compounds were characterized by single-crystal X-ray diffraction, revealing that there are two modifications of the melaminium-zinc-chloride-melamine compound, crystallizing with non-centrosymmetric space groups (<i>Pna</i>2<sub>1</sub> and <i>P</i>2<sub>1</sub>). The presence of delocalized π-electron systems in compounds containing cyclic (B<sub>3</sub>O<sub>6</sub>)<sup>3-</sup>, (C<sub>3</sub>N<sub>3</sub>O<sub>3</sub>)<sup>3-</sup>, or melamine derivatives is known to give rise to significant second harmonic generation (SHG) properties, provided that the given structure has no inversion center. All crystal structures feature Zn<sup>2+</sup> in a tetrahedral coordination environment, forming layered structures. Spectroscopic measurements on phase-pure orthorhombic (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnBr<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>) resulted in direct and indirect band gaps of 4.74 eV and 4.46 eV respectively. Measurements of the nonlinear optical response performed on single crystals of three different compounds revealed significant intensities following the sequence monoclinic (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnCl<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>) > orthorhombic (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnBr<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>) > orthorhombic (C<sub>3</sub>N<sub>6</sub>H<sub>7</sub>)ZnCl<sub>3</sub>(C<sub>3</sub>N<sub>6</sub>H<sub>6</sub>). Their SHG properties are compared with those of KTP, one of the most widely used SHG materials.

Dalton TransactionsVol. 54(48)
Institute of Inorganic Chemistry of the Slovak Academy of Sciences (SK), Czech Technical University in Prague (CZ), University of Tübingen (DE)
European Commission, Deutsche Forschungsgemeinschaft, Ministerstvo Školství, Mládeže a Tělovýchovy
Openalex Percentile: Top 77%
Nonlinear Optical Materials Research
DOIOpen Access PDFOpenAlex
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