Large Second-Harmonic Generation Responses Achieved by the Dimeric [Ge<sub>2</sub>Se<sub>4</sub>(μ-Se<sub>2</sub>)]<sup>4–</sup> Functional Motif in Polar Polyselenides A<sub>4</sub>Ge<sub>4</sub>Se<sub>12</sub> (A = Rb, Cs)
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Two new polar polyselenides Rb4Ge4Se12 (1) and Cs4Ge4Se12 (2) with rarely reported dimeric [Ge2Se4(μ-Se2)]4– units were synthesized. They present large second-harmonic generation (SHG) intensities of 7.5 and 6.5 times that of the benchmark AgGaS2 with type I phase-matching behavior, high laser-induced damaged thresholds, a wide transmission region and congruently melting behavior, making them excellent candidates for IR nonlinear optical (NLO) applications. The SHG functional motifs of both compounds are determined to be [Ge2Se4(μ-Se2)]4– unit by time-dependent density functional theory calculation, which further reveals that charge transfers from the lone pairs of terminal Se atoms to the five σ* orbitals of five-membered ring Ge2Se3 have a predominant contribution to the total SHG effect.
