Ba2M(C3N3O3)2 (M = Mg, Ca): potential UV birefringent materials with strengthened optical anisotropy originating from the (C3N3O3)3− group

Li, Zhuang; Liang, Fei; Guo, Yangwu; Lin, Zheshuai; Yao, Jiyong; Zhang, Guochun; Yin, Wenlong; Wu, Yicheng; Chen, Chuangtian

doi:10.1039/c8tc04710c

Cited by 68 publications

(55 citation statements)

References 29 publications

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“…11−22 More strikingly, cyanurates exhibit very large birefringence. For instance, Ba 2 Ca(C 3 N 3 O 3 ) 2 shows a Δn = 0.34 14 that is much greater than those of the well-known birefringent materials, such as a-BBO (Δn = 0.122 at 532 nm) 23 and CaCO 3 (Δn = 0.16 at 800 nm). 24 The birefringence of a crystal essentially comes from the anisotropic response of the electron distribution to the applied electric field.…”

Section: ■ Introductionmentioning

confidence: 99%

How To Maximize Birefringence and Nonlinearity of π-Conjugated Cyanurates

et al. 2019

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Materials with large birefringence (Δn) are highly needed by fiber-optic isolators, whereas crystals showing strong second-order harmonic generation (SHG) are the key component for all-solid-state laser devices. Cyanurate constructed by the planar π-conjugated ring (C 3 N 3 O 3 , CY) is a class of fascinating materials exhibiting not only very large Δn (larger than that of calcite) but also strong SHG (2 times that of β-BaB 2 O 4 , BBO). Here, we report five new cyanurates (I−V) and their single-crystal structures; among them, II realizes a Δn = 0.4, the maximum in the cyanurate family, and IV realizes a d 33 = 6.69 pm/V, one of the highest values in the cyanurate family. We discover a dependence between Δn and the coplanarity of the CY rings that is explicitly described by a Boltzmann function, in which the coplanarity is defined by the dihedral angle (γ) between the CY plane and the principal optical axes XY plane. II realizes the maximum Δn due to its zero γ that indicates perfect coplanarity. Such a Δn−γ dependence also allows the Δn prediction of cyanurates. Furthermore, we uncover that the SHG intensity of cyanurates increases monotonically as the angle (θ) between the maximum hyperpolarizability (β max ) vector and the crystal 2 1 polar axis decreases. We predict the d ij to extend well beyond such a value and to maximize at θ = 0°. Our results have significant implications for the future rational design and discovery of highperformance materials of π-conjugated and other related systems.

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Section: ■ Introductionmentioning

confidence: 99%

How To Maximize Birefringence and Nonlinearity of π-Conjugated Cyanurates

et al. 2019

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“…According to the UV/Vis‐IR reflectance spectra (Figure a), 1 has a high transmittance (80 %) in the wavelength above 290 nm and a wide transparency window covering from the near IR to UV spectral range. The UV absorption edge of 1 is 227 nm, corresponding to the band gap of 5.46 eV, which is comparable to those of Ba 3 (C 3 N 3 O 3 ) 2 (5.14 eV), KLHCY (5.23 eV), K 2 (HC 3 N 3 O 3 ) (4.95 eV),[18b] Ba 2 Mg(C 3 N 3 O 3 ) 2 (5.20 eV), and K 6 Cd 3 (C 3 N 3 O 3 ) 4 (5.23 eV) …”

Section: Resultsmentioning

confidence: 61%

Cs₃Na(H₂C₃N₃O₃)₄·3H₂O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units

et al. 2019

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Practical ultraviolet nonlinear optical (NLO) crystals are indispensable in modern scientific equipment and solarblind communication systems. Herein, a new hydroisocyanurate NLO crystal, Cs 3 Na(H 2 C 3 N 3 O 3 ) 4 ·3H 2 O (1), was grown by a facile aqueous solution method. It features a two-dimensional layered structure composed of coplanar large π-conjugated 2 ∞ [H 2 C 3 N 3 O 3 ]isocyanurate ribbons. More importantly, it exhibits concurrently short ultraviolet phase-matching capability (λ pm ≈ 227 nm) and considerable second-harmonic-generation [a]

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“…Traditionally, inorganic planar π-conjugated systems, including borates [17][18][19], cyanurates [20,21], carbonates [22,23], and nitrates [24,25], were excellent candidates for NLO materials because their delocalized π-conjugated groups, such as (BO 3 ) 3− , (C 3 N 3 O 3 ) 3− , (CO 3 ) 2− , and (NO 3 ) − . Generally, these units possessed high NCS possibility, strong SHG responses, wide transmittance window, and strong anisotropy [26][27][28]. For instances, KBe 2 BO 3 F 2 (KBBF) [29], Ca 3 (C 3 N 3 O 3 ) 2 [30], and β-Sr 3 (C 3 N 3 O 3 ) 2 [31], etc.…”

Section: Introductionmentioning

confidence: 99%

Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence

et al. 2022

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A new noncentrosymmetric cadmium indium borate, Cd4InO(BO3)3 (CIBO) has been successfully developed via a standard solid-state reaction. Its crystal structure was confirmed by the single crystal X-ray diffraction, which shows that CIBO belongs to the non-centrosymmetric and polar space group Cm. Its structure contains the distorted InO6 and CdOn (n = 6, 8) polyhedra, which link together by sharing an edge or corner to build a three dimensions framework with BO3 triangles accommodated in tunnels. Benefiting from the approximately parallel configuration of BO3 triangles, CIBO exhibited a strong second harmonic generation (SHG) effect (3 × KDP), and moderate birefringence of 0.077@1064 nm. Further optical and thermal characterizations suggest that CIBO possesses a wide transparent window and good thermal stability. Theoretical calculation reveals that the macroscopic SHG coefficients of CIBO results from the synergistic effect of the parallel arrangement of BO3 groups and d10 Cd2+ cation.

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Ba₂M(C₃N₃O₃)₂ (M = Mg, Ca): potential UV birefringent materials with strengthened optical anisotropy originating from the (C₃N₃O₃)³⁻ group

Abstract: (C3N3O3)3− is first proposed to be an excellent birefringent active group and the representative compounds Ba2M(C3N3O3)2 (M = Mg and Ca) are studied in detail.

Cited by 68 publications

References 29 publications

How To Maximize Birefringence and Nonlinearity of π-Conjugated Cyanurates

How To Maximize Birefringence and Nonlinearity of π-Conjugated Cyanurates

Cs₃Na(H₂C₃N₃O₃)₄·3H₂O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units

Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence

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Ba2M(C3N3O3)2 (M = Mg, Ca): potential UV birefringent materials with strengthened optical anisotropy originating from the (C3N3O3)3− group

Abstract: (C3N3O3)3− is first proposed to be an excellent birefringent active group and the representative compounds Ba2M(C3N3O3)2 (M = Mg and Ca) are studied in detail.

Cited by 68 publications

References 29 publications

How To Maximize Birefringence and Nonlinearity of π-Conjugated Cyanurates

How To Maximize Birefringence and Nonlinearity of π-Conjugated Cyanurates

Cs3Na(H2C3N3O3)4·3H2O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units

Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence

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Ba₂M(C₃N₃O₃)₂ (M = Mg, Ca): potential UV birefringent materials with strengthened optical anisotropy originating from the (C₃N₃O₃)³⁻ group

Cs₃Na(H₂C₃N₃O₃)₄·3H₂O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units