Third-Order Nonlinear Optical Behavior of an Amide-Tricarboxylate Zinc(II) Metal-Organic Framework with Two-Fold 3D+3D Interpenetration

A new metal-organic framework (MOF), [Zn4(μ4-O)(μ6-L)2(H2O)2]n·nDMF (ZSTU-10), was assembled from zinc(II) nitrate and N,N′,N″-bis(4-carboxylate)trimesicamide linkers and fully characterized. Its crystal structure discloses an intricate two-fold 3D+3D interpenetrated MOF driven by the [Zn4(μ4-O)]-based tetragonal secondary building units and the C3-symmetric tris-amide-tricarboxylate linkers (μ6-L3-). Topological analysis of ZSTU-10 reveals two interpenetrated 3,6-connected nets with an rtl (rutile) topology. Z-Scan analysis at 532 nm was conducted to study a nonlinear optical (NLO) behavior of ZSTU-10. The nonlinear responses of ZSTU-10 were explored under various laser intensities, revealing notable third-order NLO properties in the visible region. A large two-photon absorption at lower incident intensities highlights the fact that ZSTU-10 can be applied in optical limiting devices as well as optical modulators. Moreover, a nonlinear refractive index (n2) is indicative of a self-defocusing behavior. This work thus expands a family of novel MOF materials with remarkable optical properties. © 2021 American Chemical Society.

Abazari R.1, 2 , Yazdani E.2 , Nadafan M.3 , Kirillov A.M. 4, 5 , Gao J.1 , Slawin A.M.Z.6 , Carpenter-Warren C.L.6
  • 1 Institute of Functional Porous Materials, School of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou, 310018, China
  • 2 Department of Physics, Faculty of Basic Sciences, Tarbiat Modares University, Tehran, 14115-111, Iran
  • 3 Department of Physics, Faculty of Science, Shahid Rajaee Teacher Training University, Lavizan, Tehran, 16788-15811, Iran
  • 4 Centro de Química Estrutural, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisbon, 1049-001, Portugal
  • 5 Research Institute of Chemistry, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Street, Moscow, 117198, Russian Federation
  • 6 EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, United Kingdom
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