Tian, Y. B. / Li, Q. H. / Wang, Z. / Gu, Z. G. / Zhang, J. (2023)

Nano Lett. 2023, 23, 7, 3062–3069, doi.org/10.1021/acs.nanolett.3c00635

Abstract

Structural asymmetry affecting the nonlinear optics (NLO) of metal–organic frameworks (MOFs) is very important in fundamentals and applications but is still a challenge. Herein we develop a series of indium-porphyrinic framework (InTCPP) thin films and provide the first study on the coordination-induced symmetry breaking on their third-order NLO. The continuous and oriented InTCPP(H2) thin films were grown on quartz substrates and then postcoordinated with different cations (Fe2+ or Fe3+Cl–) in InTCPP(H2) (named InTCPP(Fe2+) and InTCPP(Fe3+Cl–)). The third-order NLO results reveal the Fe2+ and Fe3+Cl– coordinated InTCPP thin films have substantially enhanced NLO performance. Moreover, InTCPP(Fe3+Cl–) thin films cause symmetry breaking of microstructures, resulting in a 3-fold increase in the nonlinear absorption coefficient (up to 6.35 × 10–6 m/W) compared to InTCPP(Fe2+). This work not only develops a series of nonlinear optical MOF thin films but also provides new insight into symmetry breaking on MOFs for nonlinear optoelectronic applications.

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