Fabrication of 3D Oriented MOF Micropatterns with Anisotropic Fluorescent Properties

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2023

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Velásquez-Hernández, M.D.J.
Linares-Moreau, M.
Brandner, L.A.
Marmiroli, B.
Barella, M.
Acuna, G.P.
Zilio, S.D.
Verstreken, M.F.K.
Kravchenko, D.E.
Linder-Patton, O.M.

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Advanced Materials, 2023; 35(25):1-10

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Miriam de J. Velásquez-Hernández, Mercedes Linares-Moreau, Lea A. Brandner, Benedetta Marmiroli, Mariano Barella, Guillermo P. Acuna, Simone Dal Zilio, Margot F. K. Verstreken, Dmitry E. Kravchenko, Oliver M. Linder-Patton, Jack D. Evans, Helmar Wiltsche, Francesco Carraro, Heimo Wolinski, Rob Ameloot, Christian Doonan, and Paolo Falcaro

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Abstract

Micropatterning crystalline materials with oriented pores is necessary for the fabrication of devices with anisotropic properties. Crystalline and porous metal–organic frameworks (MOFs) are ideal materials as their chemical and structural mutability enables precise tuning of functional properties for applications ranging from microelectronics to photonics. Herein, a patternable oriented MOF film is designed: by using a photomask under X-ray exposure, the MOF film decomposes in the irradiated areas, remaining intact in the unexposed regions. The MOF film acts simultaneously as a resist and as functional porous material. While the heteroepitaxial growth from aligned Cu(OH)₂ nanobelts is used to deposit oriented MOF films, the sensitivity to radiation is achieved by integrating a brominated dicarboxylate ligand (Br₂BDC) into a copper-based MOF Cu₂L₂DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane; L = BDC/Br₂BDC). The lithographed samples act as diffraction gratings upon irradiation with a laser, thus confirming the quality of the extended MOF micropattern. Furthermore, the oriented MOF patterns are functionalized with fluorescent dyes. As a result, by rotating the polarization angle of the laser excitation, the alignment of the dye in the MOF is demonstrated. By controlling the functional response to light, this MOF patterning protocol can be used for the microfabrication of optical components for photonic devices.

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Published online: May 2, 2023

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© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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