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Second harmonic generation from symmetry breaking stimulated by mixed organic cations in zero-dimensional hybrid metal halides
Dalton Transactions ( IF 3.5 ) Pub Date : 2023-06-02 , DOI: 10.1039/d3dt01209c Jindong Cao 1 , Kunjie Liu 1 , Mingzhen Quan 1 , An Hou 1 , Xingxing Jiang 2 , Zheshuai Lin 2 , Jing Zhao 1 , Quanlin Liu 1
Dalton Transactions ( IF 3.5 ) Pub Date : 2023-06-02 , DOI: 10.1039/d3dt01209c Jindong Cao 1 , Kunjie Liu 1 , Mingzhen Quan 1 , An Hou 1 , Xingxing Jiang 2 , Zheshuai Lin 2 , Jing Zhao 1 , Quanlin Liu 1
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Mixing cations with different chemical properties to induce the generation of asymmetric structures is a new approach for tuning the optical properties of hybrid organic–inorganic metal halides (HOIMHs). In this study, zero-dimensional (C9N3H15)(C9H13SO)MBr6 (M = Bi/Sb, [C9N3H15]2+ = [(C4N2H10)(C5NH5)]2+ and [C9H14SO]+ = [CH3(C6H4)OS(CH3)2]+) are synthesized. Two different cations cause both compounds to crystallize in the polar space group P212121, thus resulting in significant phase matchable second harmonic generation under a 1064 nm laser excitation. Thus, (C9N3H15)(C9H13SO)BiBr6 and (C9N3H15)(C9H13SO)SbBr6 exhibit intensities that are approximately 1.8 and 1.7 times that of KH2PO4, respectively. The results of density functional theory calculations show that both (C9N3H15)(C9H13SO)BiBr6 and (C9N3H15)(C9H13SO)SbBr6 exhibit direct bandgaps of 2.95 and 2.81 eV, respectively. Additionally, because of the distortion of the inorganic octahedra, (C9N3H15)(C9H13SO)SbBr6 exhibited bright yellow emission at room temperature, which is attributed to ns2 fluorescence emission. We believe that the symmetry of the HOIMH crystal structure can be broken by introducing spatially differentiated bifunctional organic cations, which consequently enables even-order nonlinear activities.
中文翻译：
零维杂化金属卤化物中混合有机阳离子刺激对称性破缺产生二次谐波
混合具有不同化学性质的阳离子以诱导不对称结构的生成是调节杂化有机-无机金属卤化物（HOIMH）光学性质的新方法。本研究中，零维(C 9 N 3 H 15 )(C 9 H 13 SO)MBr 6 (M = Bi/Sb，[C 9 N 3 H 15 ] 2+ = [(C 4 N 2 H 10 )(C 5 NH 5 )] 2+和 [C 9 H 14 SO] + = [CH 3合成(C 6 H 4 )OS(CH 3 ) 2 ] + )。两种不同的阳离子导致两种化合物在极性空间群P 2 1 2 1 2 1中结晶，从而在 1064 nm 激光激发下产生显着的相位匹配二次谐波。因此，(C 9 N 3 H 15 )(C 9 H 13 SO)BiBr 6和(C 9 N 3 H 15 )(C 9 H 13 SO)SbBr 6表现出的强度分别约为KH 2 PO 4的1.8和1.7倍。密度泛函理论计算结果表明(C 9 N 3 H 15 )(C 9 H 13 SO)BiBr 6和(C 9 N 3 H 15 )(C 9 H 13 SO)SbBr 6的直接带隙均为2.95和2.81 eV，分别。另外，由于无机八面体的畸变，(C 9 N 3 H 15 )(C 9 H 13SO)SbBr 6在室温下表现出亮黄色发射，这归因于n s 2荧光发射。我们认为，通过引入空间差异的双功能有机阳离子可以打破 HOIMH 晶体结构的对称性，从而实现偶数阶非线性活动。
更新日期：2023-06-02
中文翻译：
零维杂化金属卤化物中混合有机阳离子刺激对称性破缺产生二次谐波
混合具有不同化学性质的阳离子以诱导不对称结构的生成是调节杂化有机-无机金属卤化物（HOIMH）光学性质的新方法。本研究中，零维(C 9 N 3 H 15 )(C 9 H 13 SO)MBr 6 (M = Bi/Sb，[C 9 N 3 H 15 ] 2+ = [(C 4 N 2 H 10 )(C 5 NH 5 )] 2+和 [C 9 H 14 SO] + = [CH 3合成(C 6 H 4 )OS(CH 3 ) 2 ] + )。两种不同的阳离子导致两种化合物在极性空间群P 2 1 2 1 2 1中结晶，从而在 1064 nm 激光激发下产生显着的相位匹配二次谐波。因此，(C 9 N 3 H 15 )(C 9 H 13 SO)BiBr 6和(C 9 N 3 H 15 )(C 9 H 13 SO)SbBr 6表现出的强度分别约为KH 2 PO 4的1.8和1.7倍。密度泛函理论计算结果表明(C 9 N 3 H 15 )(C 9 H 13 SO)BiBr 6和(C 9 N 3 H 15 )(C 9 H 13 SO)SbBr 6的直接带隙均为2.95和2.81 eV，分别。另外，由于无机八面体的畸变，(C 9 N 3 H 15 )(C 9 H 13SO)SbBr 6在室温下表现出亮黄色发射，这归因于n s 2荧光发射。我们认为，通过引入空间差异的双功能有机阳离子可以打破 HOIMH 晶体结构的对称性，从而实现偶数阶非线性活动。
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