Synthesis, crystal growth, linear, and nonlinear optical properties of water-grown giant optical anisotropic thiocyanates ABi(SCN)4(A = Rb, Cs)
Nguyen, Vivian Chu, Chu Sutherlin, Monique Zhang, Bingbing Wang, Jian
Nguyen, Vivian
Chu, Chu
Sutherlin, Monique
Zhang, Bingbing
Wang, Jian
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2025-12-30
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Synthesis, Crystal Growth, Linear, and Nonlinear Optical Properties of Water-Grown Giant Optical Anisotropic Thiocyanates ABi(SCN)4 (A = Rb, Cs) Vivian Nguyen, Chu Chu, Monique Sutherlin, Bingbing Zhang, and Jian Wang Crystal Growth & Design 2026 26 (2), 995-1002 DOI: 10.1021/acs.cgd.5c01614
Abstract
Thiocyanates are materials that constitute the thiocyanate anion, ([SCN])−. The linear shape of SCN– raises the chemical flexibility of the thiocyanates. More importantly, the thiocyanate crystals can be obtained in water under mild conditions. In this work, a thiocyanate system of ABi(SCN)<inf>4</inf> (A = Rb, Cs) was studied as potential nonlinear optical (NLO) materials. CsBi(SCN)<inf>4</inf> was grown as large millimeter-sized crystals in water at room temperature. The crystal structure of CsBi(SCN)<inf>4</inf> was determined by single-crystal X-ray diffraction. CsBi(SCN)<inf>4</inf> crystallizes in the orthorhombic space group P2<inf>1</inf>2<inf>1</inf>2 (No. 18) with unit cell parameters of a = 11.1943(4) Å, b= 7.8431(3) Å, and c = 6.5510(2) Å. CsBi(SCN)<inf>4</inf> is isostructural to previously reported RbBi(SCN)<inf>4</inf>. CsBi(SCN)<inf>4</inf> features a three-dimensional (3D) framework, which consists of [Bi(SCN)<inf>4</inf>] units and [Cs(SCN)<inf>4</inf>] units. The UV–Vis measurement found that CsBi(SCN)<inf>4</inf> exhibits a moderate band gap of 2.6(1) eV, which was verified by density functional theory (DFT) calculations, indicating an indirect band gap of 2.85 eV. Theoretical studies indicated that RbBi(SCN)<inf>4</inf> and CsBi(SCN)<inf>4</inf> possess large birefringence of 0.48@1064 and 0.66@546 nm, respectively. Theoretical studies verified that the Bi atoms and SCN– anions significantly contributed to the optical properties of CsBi(SCN)<inf>4</inf>. CsBi(SCN)<inf>4</inf> exhibited excellent chemical stability, which remained unchanged in air for 180 days and was verified by powder X-ray diffraction. Type-I phase-matching behavior, moderate SHG response, large birefringence, easy growth of large crystals, and high chemical stability make CsBi(SCN)<inf>4</inf> attractive as a nonlinear optical material. © 2025 American Chemical Society
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American Chemical Society
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Crystal Growth and Design
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15287483