Semi-organic nonlinear optical (NLO) materials attract growing attention due to its balanced properties and potential applications in various fields. Thiourea-coordinating metal-organic NLO material is one of the famous semi-organic systems. In our previous work, new 3BiCl3?7SC(NH2)2 (DCBPB) NLO crystals which exhibits excellent fluorescence properties and better optical transmission properties than other reported complexes of thiourea and bismuth(Ⅲ) chloride were synthesized. However, during the synthesis of DCBPB, the coexistence of BiCl3?3SC(NH2)2 (β-BTC) was found to be difficult to avoid. In order to improve the quality of the synthesized DCBPB crystals, the effects of solvent ratio, reaction temperature, and reagent ratio on the purity of DCBPB using thiourea and bismuth(III) chloride as reagents in formic acid?water solvent system were investigated. The results showed that formic acid not only depressed the hydrolysis of bismuth(III) chloride, but also improved the selectivity of DCBPB. A high selectivity of DCBPB could be achieved when the molar ratio of bismuth(III) chloride to thiourea was larger than 1:3. The reaction temperature shouldn′t exceed 50℃ to avoid side reactions. The optimization of the synthesis indicated that the hydrolysis of bismuth(III) chloride was inevitable and the highest purity of DCBPB was 89.91wt%. A two-step mechanism of DCBPB synthesis was found which included the formation of β-BTC and the conversion of β-BTC to DCBPB. Furthermore, the conversion between β-BTC and DCBPB in formic acid aqueous solution was investigated based on XRD characteristic peak area correlation. The results showed that β-BTC almost completely converted to DCBPB and no hydrolysis of bismuth(III) was detected during the conversion, a high purity of more than 98wt% was achieved via conversion of β-BTC to DCBPB in formic acid.
Yunhe BAI Tiezhu PEI Liang ZHANG Ning ZHANG Dejia MA Qiuxiang YIN Chuang XIE
. Synthesis and crystal conversion processes of nonlinear optical crystal 3BiCl3.7SC(NH2)2[J]. The Chinese Journal of Process Engineering, 2019
, 19(5)
: 1030
-1036
.
DOI: 10.12034/j.issn.1009-606X.219125
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