Third-order nonlinear optical behavior of an amide-tricarboxylate zinc(II) metal–organic framework with two-fold 3D+3D interpenetration: Inorganic Chemistry

Reza Abazari; Elnaz Yazdani; Marzieh Nadafan; Alexander M. Kirillov; Junkuo Gao; Alexandra M. Z. Slawin; Cameron L. Carpenter-Warren

doi:10.1021/acs.inorgchem.1c00997

Third-order nonlinear optical behavior of an amide-tricarboxylate zinc(II) metal–organic framework with two-fold 3D+3D interpenetration: Inorganic Chemistry

Reza Abazari, Elnaz Yazdani^*, Marzieh Nadafan, Alexander M. Kirillov^*, Junkuo Gao^*, Alexandra M. Z. Slawin, Cameron L. Carpenter-Warren

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

103 Citations (Scopus)

Abstract

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-L^3–). 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.

Original language	English
Journal	Inorganic Chemistry
Early online date	13 Jun 2021
DOIs	https://doi.org/10.1021/acs.inorgchem.1c00997
Publication status	E-pub ahead of print - 13 Jun 2021

Keywords

Ligands
Nonlinear optics
Metal organic frameworks
Optical properties
Lasers

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10.1021/acs.inorgchem.1c00997

CCDC 2001565: Experimental Crystal Structure Determination
Abazari, R. (Creator), Yazdani, E. (Creator), Nadafan, M. (Creator), Kirillov, A. M. (Creator), Gao, J. (Creator), Slawin, A. M. Z. (Creator) & Carpenter-Warren, C. L. (Creator), Cambridge Crystallographic Data Centre, 9 Apr 2021
DOI: 10.5517/ccdc.csd.cc255sms
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Abazari, R., Yazdani, E., Nadafan, M., Kirillov, A. M., Gao, J., Slawin, A. M. Z., & Carpenter-Warren, C. L. (2021). Third-order nonlinear optical behavior of an amide-tricarboxylate zinc(II) metal–organic framework with two-fold 3D+3D interpenetration: Inorganic Chemistry. Inorganic Chemistry. Advance online publication. https://doi.org/10.1021/acs.inorgchem.1c00997

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title = "Third-order nonlinear optical behavior of an amide-tricarboxylate zinc(II) metal–organic framework with two-fold 3D+3D interpenetration: Inorganic Chemistry",

abstract = "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.",

keywords = "Ligands, Nonlinear optics, Metal organic frameworks, Optical properties, Lasers",

author = "Reza Abazari and Elnaz Yazdani and Marzieh Nadafan and Kirillov, {Alexander M.} and Junkuo Gao and Slawin, {Alexandra M. Z.} and Carpenter-Warren, {Cameron L.}",

note = "This work has been supported by the Tarbiat Modares University. The authors are grateful for the financial support. A.M.K. acknowledges the FCT (LISBOA-01-0145-FEDER029697 and PTDC/QUI-QIN/3898/2020) and RUDN University (this paper has been supported by the RUDN University Strategic Academic Leadership Program).",

year = "2021",

month = jun,

day = "13",

doi = "10.1021/acs.inorgchem.1c00997",

language = "English",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society (ACS)",

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TY - JOUR

T1 - Third-order nonlinear optical behavior of an amide-tricarboxylate zinc(II) metal–organic framework with two-fold 3D+3D interpenetration

T2 - Inorganic Chemistry

AU - Abazari, Reza

AU - Yazdani, Elnaz

AU - Nadafan, Marzieh

AU - Kirillov, Alexander M.

AU - Gao, Junkuo

AU - Slawin, Alexandra M. Z.

AU - Carpenter-Warren, Cameron L.

N1 - This work has been supported by the Tarbiat Modares University. The authors are grateful for the financial support. A.M.K. acknowledges the FCT (LISBOA-01-0145-FEDER029697 and PTDC/QUI-QIN/3898/2020) and RUDN University (this paper has been supported by the RUDN University Strategic Academic Leadership Program).

PY - 2021/6/13

Y1 - 2021/6/13

N2 - 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.

AB - 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.

KW - Ligands

KW - Nonlinear optics

KW - Metal organic frameworks

KW - Optical properties

KW - Lasers

U2 - 10.1021/acs.inorgchem.1c00997

DO - 10.1021/acs.inorgchem.1c00997

M3 - Article

SN - 0020-1669

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -

Third-order nonlinear optical behavior of an amide-tricarboxylate zinc(II) metal–organic framework with two-fold 3D+3D interpenetration: Inorganic Chemistry

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CCDC 2001565: Experimental Crystal Structure Determination

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