KLi(HC3N3O3)Â·2H2O: Solvent-drop Grinding Method Towards the

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KLi(HC3N3O3)·2H2O: Solvent-drop Grinding Method Towards the Hydro-isocyanurate Nonlinear Optical Crystal Donghong Lin, Min Luo, Chen-Sheng Lin, Feng Xu, and Ning Ye J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 12 Feb 2019 Downloaded from http://pubs.acs.org on February 12, 2019

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Journal of the American Chemical Society

KLi(HC3N3O3)·2H2O: Solvent-drop Grinding Method Towards the Hydro-isocyanurate Nonlinear Optical Crystal Donghong Lin,†,‡ Min Luo,*,† Chensheng Lin†, Feng Xu†,‡ and Ning Ye*,† Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China †

‡University

of Chinese Academy of Sciences, Beijing 100049, China

Supporting Information ABSTRACT: A novel mixed alkali hydro-isocyanurate, KLi(HC3N3O3)·2H2O was firstly prepared in AOH-BOHH3C3N3O3 (A/B = Li/Na/K/Rb/Cs) system via a solvent-drop grinding method. KLi(HC3N3O3)·2H2O shows a large second harmonic generation response (5.3×KH2PO4) with an ultraviolet cutoff edge of 237 nm. More importantly, the bulk single crystal can be readily grown through water solution technique. Characterization of these crystals indicates that KLi(HC3N3O3)·2H2O has a high laser damage threshold (LDT) (4.76 GW/cm2) and exhibits a large birefringence (∆n=0.186@514 nm), which reduces Type I phase-matching to 246 nm.

Ultraviolet (UV) nonlinear optical (NLO) crystals, which can generate ultraviolet laser by second-harmonic generation (SHG) process, have caught continuous attention by reason of their outstanding applications in laser and optical communication industry.1-6 Up to now, the reported superior UV NLO materials are mostly borates. According to the anionic groups, fundamental building blocks (FBBs) of borate crystals can be classified into three main categories, namely CsB3O5 (CBO)7 and LiB3O5 (LBO)8 with (B3O7)5− group, β-BaB2O4 (BBO)9 with (B3O6)3− group, and KBe2BO3F2 (KBBF)10-11, K2Al2B2O7 (KABO)12, Sr2Be2B2O7 (SBBO)13 and Pb2BO3Cl14 with (BO3)3− group. Among them, since the (B3O6)3− unit with a large π-conjugation has a large birefringence and remarkable microscopic second-order susceptibility, it has been fully regarded as an ideal FBBs for constructing UV NLO crystals. In recent years, Meyer et al. discovered that the (C3N3O3)3- unit in inorganic metal cyanurates exhibited isoelectric and highly similar structural to the (B3O6)3unit. Meanwhile, they successfully employed (C3N3O3)3- unit to synthesize β-Sr3(C3N3O3)2 and Ca3(C3N3O3)2,15-16 which are isostructural to BBO but exhibit larger birefringence and stronger SHG coefficients compared with BBO. More recently, Liang et al. confirmed the large π–conjugated (C3N3O3)3− group is indeed a superior NLO-active unit in theory.17 Up to date, however, there are very few reports on new inorganic cyanurate NLO crystals,15-16, 18-20 which could be attributed to the harsh reaction conditions for single crystal growth. The synthesis of these metal cyanurates involves the cyclo-trimerization reaction of (OCN)− and the substitutional reaction of a metal halide with an alkali metal cyanate under the vacuum condition.21 It is well known that, apart from cyanurates, hydro-isocyanurates or dihydroisocyanurates have a large π-conjugated (HC3N3O3)2– or (H2C3N3O3)– group. Therefore, noncentrosymmetric (NCS) hydro-

isocyanurates or dihydro-isocyanurates can be expected to have large SHG coefficients and large birefringence. In particularly, hydro-isocyanurates or dihydro-isocyanurates are commonly obtained from aqueous solution under mild reaction conditions,2227 which contribute to their bulk size crystal growth. Thus, it is of great significance to explore hydro-isocyanurates or dihydroisocyanurates as UV NLO materials. In addition to isocyanurates, alkali metals were selected as the counter cations to explore UV NLO crystals because the alkali metal-oxygen bonds do not have absorption in the UV region.28-32 Although more than fifteen alkali isocyanurates have been reported, they are either lack of single crystal data or centrosymmetric compounds without SHG effects. Therefore, it is imperative to develop a practical way for the synthesis of new NCS alkali metal isocyanurates as candidates of UV NLO crystals. Solvent-drop grinding method is a feasible protocol to synthesize organic co-crystals materials from solid organic acid systems, such as cyanuric acid.33 However, some co-crystals are difficult to synthesis even after sufficient grinding.34-35 Moreover, most cocrystals are chemically unstable because of their weak intermolecular interaction. Given the neutralization reaction can form a strong chemical bond between cation and anion groups, we proposed that the combination of neutralization reaction with the solvent-drop grinding method may be an effective way to synthesize novel inorganic-organic NLO crystals with high chemical stability, such as alkali isocyanurates.

Figure 1, The centimeter-lever single crystals of KLHCY in AOH-BOH-H3C3N3O3 (A/B = Li/Na/K/Rb/Cs) system. In the synthesis of twenty potential alkali isocyanurate powder AH2C3N3O3·xH2O or ABHC3N3O3·xH2O (A/B = Li/Na/K/Rb/Cs), the reaction mixtures of AOH, BOH, and H3C3N3O3 were directly ground at ambient temperature with or without adding water/ethanol in a stoichiometric ratio (see Supporting Information for details). Those samples obtained by adding ethanol as grinding aid had better SHG responses and clearer powder X-ray diffraction (PXRD) patterns. Moreover, the PXRD and powder SHG (PSHG)

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measurement revealed the presence of pure, stable, and unprecedented compounds with NCS structure, including KLiHC3N3O3·xH2O, RbLiHC3N3O3·xH2O, RbNaHC3N3O3·xH2O and CsNaHC3N3O3·xH2O. These preliminary results encouraged us to grow single crystal for determining the structure. As a result, the mixed alkali hydro-isocyanurate KLiHC3N3O3·xH2O was identified as KLi(HC3N3O3)·2H2O (KLHCY). Moreover, centimeter-level KLHCY single crystals were readily grown via water solution method (Figure S1). The obtained bulk KLHCY crystals with the dimension of 10 mm × 15 mm × 6 mm can be washed with acetone (Figure 1). The existence of potassium, carbon, nitrogen, and oxygen elements were confirmed by energydispersive X-ray spectroscopy (Figure S2). Currently, the investigation of other alkali isocyanurates synthesized via this method is undergoing. KLHCY crystallizes in non-centrosymmetric space group Pna21, which is the same as LBO.36 In the structure of KLHCY (Figure 2a), the basic structural unit is a hydro-isocyanurate (HC3N3O3)2- group (Figure 2b), which shows typical bond angles (118.5-123.2° for C-N-C and 116.8-123.2° for O-C-N) and typical bond distances (1.20-1.29 Å for C-O and 1.31-1.38 Å for C-N). Also, a single crystallographically independent Li atom is presented in this asymmetric unit, which is associated with four O atoms to form a distorted tetrahedron LiO4 (Figure 2c) configuration with Li-O bond distances of 1.93-2.13 Å. The LiO4 polyhedral interconnect into a 1D chain via shared corners, which further bridge via (HC3N3O3)2- groups to construct an intricate 2D [Li(HC3N3O3)O]- layer. Therefore, the structure of KLHCY can be described as 2D wavy [Li(HC3N3O3)O]- layers separated by K atoms and water molecules.

could generate coherent light above 250 nm through frequency conversion without significant absorption loss. Also, the UV absorption edge of KLHCY is 237 nm (correspond to 5.23 eV), which is in line with the calculated band gap of 5.15 eV (Figure S4). Moreover, the calculated partial and total densities of states indicate that the optical properties of KLHCY are primarily attributed to (HC3N3O3)2– groups (Figure S5).

Figure 3, (a) The ultraviolet-visible-near-infrared transmittance spectrum of KLHCY crystal wafer. (b) The refractive indices of KLHCY single crystal. (c) The convergent polarized light interference pattern of KLHCY crystal along the axis of b; (d) and along the axis of b with 45-degree rotation. To obtain a coherent light output, chromatic dispersion and birefringence are critical to achieve phase-matching (PM).39 To determine the birefringence, we have measured the refractive indexes of suitable KLHCY crystals based on the prism-coupling technique at ﬁve different wavelengths (407, 514, 636, 965 and 1547 nm). And then, the refractive indices of KLHCY were fitted to ni2= A + B / (λ2 − C) – Dλ2 (Sellmeier equations), where A-D are the parameters while λ is the wavelength in microns (Figure 3b).

0.01060  0.01301  2 (  0.04508) 0.02243  0.02809   2 n Y2  2.69313  2 (  0.04043) 0.02589  0.02462   2 n 2Z  2.68570  2 (  0.03419) n 2X  2.17023 

Figure 2, (a) Crystal structure of KLHCY; (b) The layers of KLHCY consisting of (HC3N3O3) triangular entities, and (c) (LiO4) polyhedral. The thermogravimetry plot (Figure S3) of KLHCY exhibited two major steps of weight loss from 30°C to 600°C, which is very similar to other hydro-isocyanurates.25 The first stages of weight loss in the temperature interval of 125−140 °C was 16.38% (cal. 16.84%), accounting for the loss of two water molecule of crystallization. The second stages of mass loss in the temperature interval of 402-409 °C was 20.19% (cal. 20.57%), accounting for the loss of cyanic acid molecule from (HC3N3O3)2- group. Notably, although KLHCY decomposes at 125°C because of the water of crystallization, it has a high LDT values of 4.76 GW/cm2@1064 nm (10 Hz, 5 ns), which is comparable with some commercialized NLO crystals37-38. The ultraviolet-visible-near-infrared transmittance spectra were measured (Figure 3a) by a polished wafer of KLHCY crystal (Figure 3a, inset). Obviously, KLHCY exhibited wide transparency windows greater than 60%, from 250 to 800 nm, indicating that it

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Notably, even though KLHCY is a biaxial crystal that can be proved by the convergent light interference patterns (Figure 3c, in which there are two typical biaxial crystal features, namely the “maltese cross” pattern with two visible different width curved isogyres and the isochrones exhibiting the “∞” character pattern), the measured refractive indices nz are almost equal to ny. This result is very close to the characteristics of the uniaxial crystal. To explain this phenomenon, the conoscopic interference pattern was employed. In the 45 degrees rotated interference pattern (Figure 3d), the points where the isogyres are most tightly curved, OA1 and OA2, are the positions of two optic axes. Since the flexibility of isogyres curve has the negative correlation with the 2V angle (the angle between two optic axes), the isogyres curve is close to 90°, indicating that the 2V angle is very small. This result suggests that two optic axes are very close, which consequently result in the KLHCY exhibiting the similar refractive index characteristics to those of uniaxial crystal.


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Journal of the American Chemical Society Meanwhile, the dense interferometric fringes show KLHCY has a large birefringence. Accurately, the birefringence of KLHCY (0.186@514 nm) was approximately equal to those of typical birefringent materials, such as CaCO3 (0.172@589 nm)40, YVO4 (0.226@590 nm)41, MgF2 ([email protected] nm)42, BBO (0.119@546 nm)43 and larger than those of recorded UV/deep-UV birefringent crystals, like Na3Ba2(B3O6)2F (0.115@532 nm)44, Ba2Ca(B3O6)2 (0.124@589 nm)45, Ca3(BO3)2 (0.097@589 nm)46. In the light of anionic group theory, the contribution to large birefringence in KLHCY should stem from the (HC3N3O3)2- groups. This large birefringence value of KLHCY indicates that the (HC3N3O3)2group may be an excellent FBB to build UV birefringent materials. Besides, large birefringence of KLHCY could make the crystal satisfy the phase matching condition at short wavelength. Furthermore, the PM curves (Figure S6) were calculated based on the refractive indices of KLHCY. KLHCY could realize PM of both type I and type II, and the shortest phase matching double frequency wavelength was reduced to 246 nm. These results demonstrated that the shortest λPM of KLHCY is fully comparable to some well-known UV NLO materials, including KH2PO4 (KDP) (258 nm)47, LBO (277 nm)48, CsLiB6O10 (CLBO) (237 nm)48, and K3B6O10Cl (255 nm)49. The finding of this study suggests that KLHCY possesses prominent UV PM capabilities, which enable it as one of several bulk NLO crystals that could generate laser below 266 nm through a direct double frequency process.

KLi(HC3N3O3)·2H2O indicated that it has promising potentials in the UV NLO applications owing to its large birefringence (∆n=0.186), high SHG coefficients (d33 > 5 × KDP), easy growth of large single crystals, wide band gaps (Eg > 5.0 eV) and stability in air at room temperature. More importantly, our study revealed that (HC3N3O3)2– anion group is also an outstanding fundamental building block for UV NLO crystals. Therefore, exploring novel UV NLO crystals containing (H2C3N3O3)–, (HC3N3O3)2– anions, or other solid organic acid anions prepared via the solvent-drop grinding method is worthy of further research.

ASSOCIATED CONTENT Supporting Information Methods, synthesis and additional tables/figures and CIF data is available at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *[email protected] *[email protected]

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT

Figure 4, (a) PSHG measurements of KLHCY at 1064 nm (b) and 532 nm. The powder SHG measurement on KLHCY was performed under 532 nm and 1064 nm laser, separately (Figures 4a, 4b). As particle sizes increasing, the SHG intensities increase at both wavelengths, suggesting the phase-matching behavior of KLHCY. Meanwhile, this result can support the above-mentioned PM calculations of KLHCY. The SHG intensity of KLHCY was about 0.8 times of BBO at 532 nm and 5.3 times of KDP at 1064 nm. The powder SHG response was larger than those of reported UV/deepUV NLO materials, such as SrB5O7F3 (2.5×KDP)50, NH4B4O6F (3 ×KDP)51, CsSiB3O7 (0.8×KDP)52, RbCaCO3F (1.11×KDP)53, Na2Ca2(CO3)3 (3 × KDP)54, LiRb2PO4 (2.1 × KDP)55, and CsMgPO4·6H2O (1.1 × KDP)56. The “velocity-gauge” formula57 was used to calculated the theoretical values of NLO coefficients. The calculated largest tensor component of KLHCY was d33 at 1064 nm, which agreed well with the geometrical factor (Table S1). This result further demonstrated that the (HC3N3O3)2– groups come to dominate the SHG response of KLHCY. Besides, it is noteworthy that, in this example, (HC3N3O3)2- groups are not coplanar or parallel to each other (Figure S7 in the Supporting Information). If cations with suitable radius are selected to make the (HC3N3O3)2- groups coplanar and parallel alignment, a larger SHG effect, even greater than that of BBO, could be expected. In summary, a new mixed alkali hydro-isocyanurate, KLi(HC3N3O3)·2H2O, was synthesized and characterized. Meanwhile, the preliminary study demonstrated that solvent-drop grinding method might be an effective way to synthesize novel inorganic-organic NLO crystals from solid organic acid system. The ﬁrst exploratory investigations on NLO properties of

This work was supported by the National Natural Science Foundation of China (Grant Nos. 51890862, U1605245 and 51425205), the National Key Research and Development Plan of Ministry of Science and Technology (Grant No. 2016YFB0402104), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB20000000) and Youth Innovation Promotion Association CAS. We thank Professor Shilie Pan, Miriding Mutailipu at XTIPC.CAS for their help with refractive index measurements. And we thank Professor Jianggao Mao, Jianghe Feng, Jin Chen at FJIRSM for their help with 532nm PSHG tests. And we thank Professor Xinxin Zhuang, Liwang Ye, Bowen Huang, Xumin Chai at FJIRSM for their help with water solution method. And we thank Professor Xifa Long, Bin Su at FJIRSM for their help with convergent light test.

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KLi(HC3N3O3)Â·2H2O: Solvent-drop Grinding Method Towards the

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