Determining Structures of Layer-by-Layer Spin-Coated Zinc Dicarboxylate-Based Metal-Organic Thin Films.

Autor: Fischer JC; Institute of Microstructure Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany., Steentjes R; Institute for Solid-State Physics, NAWI Graz, Graz University of Technology, Petersgasse 16/II, 8010, Graz, Austria., Chen DH; Institute of Functional Interfaces, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany., Richards BS; Institute of Microstructure Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.; Light Technology Institute, Karlsruhe Institute of Technology, Engesserstrasse 13, 76131, Karlsruhe, Germany., Zojer E; Institute for Solid-State Physics, NAWI Graz, Graz University of Technology, Petersgasse 16/II, 8010, Graz, Austria., Wöll C; Institute of Functional Interfaces, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany., Howard IA; Institute of Microstructure Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.; Light Technology Institute, Karlsruhe Institute of Technology, Engesserstrasse 13, 76131, Karlsruhe, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jul 02; Vol. 30 (37), pp. e202400565. Date of Electronic Publication: 2024 Jun 17.
DOI: 10.1002/chem.202400565
Abstrakt: Thin films of crystalline solids with substantial free volume built from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn-based SBUs are especially relevant in this case because they avoid quenching the chromophore's luminescence. We find that layer-by-layer spin-coating using Zn acetate dihydrate and benzene-1,4-dicarboxylic acid (H 2 BDC) and biphenyl-4,4'-dicarboxylic acid (H 2 BPDC) linkers readily produces crystalline thin films. However, analysis of the grazing-incidence wide-angle X-ray scattering (GIWAXS) data reveals the structures of these films vary significantly with the linker, and with the metal-to-linker molar ratio used for fabrication. Under equimolar conditions, H 2 BPDC creates a type of structure like that proposed for SURMOF-2, whereas H 2 BDC generates a different metal-hydroxide-organic framework. Large excess of Zn 2+ ions causes the growth of layered zinc hydroxides, irrespective of the linker used. Density functional theory (DFT) calculations provide structural models with minimum total energy that are consistent with the experimentally observed diffractograms. In the broader sense, this work illustrates the importance in this field of careful structure determination, e. g., by utilizing GIWAXS and DFT simulations to determine the structure of the obtained crystalline metal-organic thin films, such that properties can be rationally engineered and explained.
(© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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