Elevating the optical nonlinearity: design, synthesis, and properties of a mixed-ligand zinc(II) metal–organic framework

Reza  Abazari; Soheila  Sanati; Marzieh  Nadafan; David B. Cordes; Alexandra M. Z. Slawin; Alexander M.  Kirillov

doi:10.1021/acsami.4c22681

Elevating the optical nonlinearity: design, synthesis, and properties of a mixed-ligand zinc(II) metal–organic framework

Reza Abazari, Soheila Sanati, Marzieh Nadafan, David B. Cordes, Alexandra M. Z. Slawin, Alexander M. Kirillov

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

Abstract

The molecular design of new compounds with enhanced third-order nonlinear optical (NLO) applications is an important research topic in the area of functional materials. The present study describes a new 3D metal–organic framework [Zn₃(μ₃-bta)₂(μ₄-ata)₂]_n (abbreviated as NH₂–Zn-MUM-6), generated solvothermally from a multicomponent system composed of zinc(II) ions and 2-aminoterephthalic acid (H₂ata) and 1H-benzotriazole (Hbta) as linkers. Apart from an intricate porous structure with a seh-4,6-Imma topology, this MOF features good thermal stability and exceptional NLO characteristics. These were investigated in detail by a Z-scan method, revealing the remarkably high values of third-order nonlinear refractive index (n₂ = 30.83 × 10^–8 cm²/W) and nonlinear absorption coefficient (β = 4.06 × 10^–4 cm/W). An extended π-conjugation in both aromatic ligands, μ₃-bta^– and μ₄-ata^2–, and their interaction with Zn centers contribute to the formation of a highly polarizable system, thus significantly enhancing its capacity for NLO behavior. This study broadens the family of nonlinear optical materials and provides insights into the relationship between the structure and properties of amino-functionalized mixed-linker MOFs from the viewpoint of optical applications such as all-optical switching and data transmission.

Original language	English
Number of pages	9
Journal	ACS Applied Materials & Interfaces
Volume	Ahead of Print
Early online date	4 Mar 2025
DOIs	https://doi.org/10.1021/acsami.4c22681
Publication status	E-pub ahead of print - 4 Mar 2025

Keywords

Coordination polymers
Functional materials
Nonlinear optical materials
Two-photon absorption
Third-harmonic generation

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10.1021/acsami.4c22681

Abazari_2025_AMaI_Elevating-optical-nonlinearity-zinc(II)-metal-organic-framework_AAM_CCBY
Copyright © 2025 the Authors. This work has been made available online in accordance with the University of St Andrews Open Access policy. This accepted manuscript is distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. The final published version of this work is available at https://doi.org/10.1021/acsami.4c22681
Accepted author manuscript, 1.41 MBLicence: CC BY

CCDC 2365799: Experimental Crystal Structure Determination
Abazari, R. (Creator), Sanati, S. (Creator), Nadafan, M. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator), Safin6, D. A. (Creator) & Liu, M. (Creator), Cambridge Crystallographic Data Centre, 2024
DOI: 10.5517/ccdc.csd.cc2kdt3x
Dataset

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@article{345dfd8e400f4186a46f90c6f2484727,

title = "Elevating the optical nonlinearity: design, synthesis, and properties of a mixed-ligand zinc(II) metal–organic framework",

abstract = "The molecular design of new compounds with enhanced third-order nonlinear optical (NLO) applications is an important research topic in the area of functional materials. The present study describes a new 3D metal–organic framework [Zn3(μ3-bta)2(μ4-ata)2]n (abbreviated as NH2–Zn-MUM-6), generated solvothermally from a multicomponent system composed of zinc(II) ions and 2-aminoterephthalic acid (H2ata) and 1H-benzotriazole (Hbta) as linkers. Apart from an intricate porous structure with a seh-4,6-Imma topology, this MOF features good thermal stability and exceptional NLO characteristics. These were investigated in detail by a Z-scan method, revealing the remarkably high values of third-order nonlinear refractive index (n2 = 30.83 × 10–8 cm2/W) and nonlinear absorption coefficient (β = 4.06 × 10–4 cm/W). An extended π-conjugation in both aromatic ligands, μ3-bta– and μ4-ata2–, and their interaction with Zn centers contribute to the formation of a highly polarizable system, thus significantly enhancing its capacity for NLO behavior. This study broadens the family of nonlinear optical materials and provides insights into the relationship between the structure and properties of amino-functionalized mixed-linker MOFs from the viewpoint of optical applications such as all-optical switching and data transmission.",

keywords = "Coordination polymers, Functional materials, Nonlinear optical materials, Two-photon absorption, Third-harmonic generation",

author = "Reza Abazari and Soheila Sanati and Marzieh Nadafan and Cordes, {David B.} and Slawin, {Alexandra M. Z.} and Kirillov, {Alexander M.}",

note = "Funding: This work was supported by University of Maragheh, Iran{\textquoteright}s National Elites Foundation and Iran National Science Foundation (project number: 4037973); the authors are also grateful for the financial support. AMK acknowledges the FCT, Portugal (projects PTDC/QUI-QIN/3898/2020, UIDB/00100/2020, and LA/P/0056/2020).",

year = "2025",

month = mar,

day = "4",

doi = "10.1021/acsami.4c22681",

language = "English",

volume = "Ahead of Print",

journal = "ACS Applied Materials & Interfaces",

issn = "1944-8244",

publisher = "American Chemical Society (ACS)",

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TY - JOUR

T1 - Elevating the optical nonlinearity

T2 - design, synthesis, and properties of a mixed-ligand zinc(II) metal–organic framework

AU - Abazari, Reza

AU - Sanati, Soheila

AU - Nadafan, Marzieh

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Kirillov, Alexander M.

N1 - Funding: This work was supported by University of Maragheh, Iran’s National Elites Foundation and Iran National Science Foundation (project number: 4037973); the authors are also grateful for the financial support. AMK acknowledges the FCT, Portugal (projects PTDC/QUI-QIN/3898/2020, UIDB/00100/2020, and LA/P/0056/2020).

PY - 2025/3/4

Y1 - 2025/3/4

N2 - The molecular design of new compounds with enhanced third-order nonlinear optical (NLO) applications is an important research topic in the area of functional materials. The present study describes a new 3D metal–organic framework [Zn3(μ3-bta)2(μ4-ata)2]n (abbreviated as NH2–Zn-MUM-6), generated solvothermally from a multicomponent system composed of zinc(II) ions and 2-aminoterephthalic acid (H2ata) and 1H-benzotriazole (Hbta) as linkers. Apart from an intricate porous structure with a seh-4,6-Imma topology, this MOF features good thermal stability and exceptional NLO characteristics. These were investigated in detail by a Z-scan method, revealing the remarkably high values of third-order nonlinear refractive index (n2 = 30.83 × 10–8 cm2/W) and nonlinear absorption coefficient (β = 4.06 × 10–4 cm/W). An extended π-conjugation in both aromatic ligands, μ3-bta– and μ4-ata2–, and their interaction with Zn centers contribute to the formation of a highly polarizable system, thus significantly enhancing its capacity for NLO behavior. This study broadens the family of nonlinear optical materials and provides insights into the relationship between the structure and properties of amino-functionalized mixed-linker MOFs from the viewpoint of optical applications such as all-optical switching and data transmission.

AB - The molecular design of new compounds with enhanced third-order nonlinear optical (NLO) applications is an important research topic in the area of functional materials. The present study describes a new 3D metal–organic framework [Zn3(μ3-bta)2(μ4-ata)2]n (abbreviated as NH2–Zn-MUM-6), generated solvothermally from a multicomponent system composed of zinc(II) ions and 2-aminoterephthalic acid (H2ata) and 1H-benzotriazole (Hbta) as linkers. Apart from an intricate porous structure with a seh-4,6-Imma topology, this MOF features good thermal stability and exceptional NLO characteristics. These were investigated in detail by a Z-scan method, revealing the remarkably high values of third-order nonlinear refractive index (n2 = 30.83 × 10–8 cm2/W) and nonlinear absorption coefficient (β = 4.06 × 10–4 cm/W). An extended π-conjugation in both aromatic ligands, μ3-bta– and μ4-ata2–, and their interaction with Zn centers contribute to the formation of a highly polarizable system, thus significantly enhancing its capacity for NLO behavior. This study broadens the family of nonlinear optical materials and provides insights into the relationship between the structure and properties of amino-functionalized mixed-linker MOFs from the viewpoint of optical applications such as all-optical switching and data transmission.

KW - Coordination polymers

KW - Functional materials

KW - Nonlinear optical materials

KW - Two-photon absorption

KW - Third-harmonic generation

U2 - 10.1021/acsami.4c22681

DO - 10.1021/acsami.4c22681

M3 - Article

SN - 1944-8244

VL - Ahead of Print

JO - ACS Applied Materials & Interfaces

JF - ACS Applied Materials & Interfaces

ER -

Elevating the optical nonlinearity: design, synthesis, and properties of a mixed-ligand zinc(II) metal–organic framework

Abstract

Keywords

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CCDC 2365799: Experimental Crystal Structure Determination

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