Maximizing Conversion of Surface Click Reactions for Versatile Molecular Modification on Metal Oxide Nanowires

Yamaguchi, Rimon; Hosomi, Takuro; Otani, Masaya; Nagashima, Kazuki; Takahashi, Tetsuo; Zhang, Guozhu; Kanai, Masaki; Masai, Hiroshi; Terao, Jun; Yanagida, Takeshi

doi:10.1021/acs.langmuir.1c00106

Cited by 6 publications

(7 citation statements)

References 37 publications

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“…It should be noted that we selected the lowest possible temperature for each ALD precursor within the range provided by the manufacturer of the ALD equipment used in this study to minimize the thermal decomposition of the SAM skeletons. All the used temperatures (150 or 200 °C) are sufficiently low since the alkyl skeletons are reported to begin decomposing at around 250 °C …”

Section: Methodsmentioning

confidence: 99%

“…This is mainly due to the lack of comprehensive studies of ALD processes on organic molecules. ,− One of the major reasons for this is the difficulty to perform morphological analysis [e.g., transmission electron microscopy (TEM) , ], spectroscopic reaction tracking [e.g., Fourier-transformed infrared spectroscopy (FT-IR) , ], and quantitative deposition monitoring [e.g., quartz crystal microbalance (QCM) − ] on the identical sample. Recently, we developed single-crystal oxide nanowires as a comprehensive platform for these analyses. − The arrays of the single-crystal nanowires are suitable for FT-IR and QCM because their large surface area can significantly amplify signals obtained from small amounts of monolayer compounds. At the same time, each nanowire has flat single-crystal facets with well-defined edges, making it possible to observe precisely aligned cross-sections by scanning TEM (STEM) without complex destructive procedures including etching and milling.…”

Section: Introductionmentioning

confidence: 99%

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Interfacial Molecular Compatibility for Programming Organic–Metal Oxide Superlattices

Ono

Mitamura

Hosomi

et al. 2023

ACS Appl. Mater. Interfaces

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Artificially programming a sequence of organic–metal oxide multilayers (superlattices) by using atomic layer deposition (ALD) is a fascinating and challenging issue in material chemistry. However, the complex chemical reactions between ALD precursors and organic layer surfaces have limited their applications for various material combinations. Here, we demonstrate the impact of interfacial molecular compatibility on the formation of organic–metal oxide superlattices using ALD. The effects of both organic and inorganic compositions on the metal oxide layer formation processes onto self-assembled monolayers (SAM) were examined by using scanning transmission electron microscopy, in situ quartz crystal microbalance measurements, and Fourier-transformed infrared spectroscopy. These series of experiments reveal that the terminal group of organic SAM molecules must satisfy two conflicting requirements, the first of which is to promptly react with ALD precursors and the second is not to bind strongly to the bottom metal oxide layers to avoid undesired SAM conformations. OH-terminated phosphate aliphatic molecules, which we have synthesized, were identified as one of the best candidates for such a purpose. Molecular compatibility between metal oxide precursors and the −OHs must be properly considered to form superlattices. In addition, it is also important to form densely packed and all-trans-like SAMs to maximize the surface density of reactive −OHs on the SAMs. Based on these design strategies for organic–metal oxide superlattices, we have successfully fabricated various superlattices composed of metal oxides (Al-, Hf-, Mg-, Sn-, Ti-, and Zr oxides) and their multilayered structures.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Interfacial Molecular Compatibility for Programming Organic–Metal Oxide Superlattices

Ono

Mitamura

Hosomi

et al. 2023

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

show abstract

“…Recently, we have developed single-crystal oxide nanowires as a comprehensive platform for these analyses. [34][35][36] The arrays of the single-crystal nanowires are suitable for FT-IR and QCM because their large surface area can significantly amplify signals obtained from small amounts of monolayer compounds.…”

Section: Table Of Contents (Toc) Introductionmentioning

confidence: 99%

Interfacial Molecular Compatibility for Programming Organic-Metal Oxide Superlattices

Ono

Mitamura

Hosomi

et al. 2023

Preprint

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Programming artificially a sequence of organic-metal oxide multilayers (superlattices) by using atomic layered depositions (ALD) is a fascinating and challenging issue in material chemistry. However, the complex chemical reactions between ALD precursors and organic layer surfaces have limited their applications for various material combinations. Here we demonstrate the impact of interfacial molecular compatibility on the formation of organic-metal oxide superlattices using ALD. The effects of both organic and inorganic compositions on the metal oxide layer formation processes onto self-assembled monolayers (SAM) were examined by using scanning transmission electron microscopy (STEM), in-situ quartz crystal microbalance (QCM) measurements, and Fourier-transformed infrared spectroscopy (FT-IR). These series of experiments reveal that the terminal group of organic SAM molecules must satisfy two conflicting requirements, the first of which is to promptly react with ALD precursors and the second is not to bind strongly to the bottom metal oxide layers to avoid undesired SAM conformations. OH-terminated phosphate aliphatic molecules, which we have synthesized, were identified as one of the best candidates for such a purpose. Molecular compatibility between metal oxide precursors and the -OHs must be properly considered to form superlattices. In addition, it is also important to form densely packed and all-trans-like SAMs to maximize the surface density of reactive -OHs on the SAMs. Based on these design strategies for organic-metal oxide superlattices, we have successfully fabricated various superlattices composed of metal oxides (Al-, Hf-, Mg-, Sn-, Ti-, Zr oxides) and their multilayered structures.

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“…In 2001, Sharpless and co-workers developed “click” chemistry that enables the formation of 1,2,3-triazole compounds, and since then, the method has been widely used for synthetic chemistry. − The reaction has two product possibilities: 1,4-disubstituted and 1,5-disubstituted triazoles. Different catalysts can yield either regioisomers or a mixture of both. − The two isomers possess completely different chemical properties in solution and thus have different applications. − …”

Section: Introductionmentioning

confidence: 99%

“…In parallel with advancement in azide–alkyne click reactions in solution, click reactions on surfaces became important for a range of applications including biological, pharmaceutical, − and material science. ,− To the best of our knowledge, all surface-based click reactions, to date, are based on copper Cu(I) catalysis, which produces exclusively the 1,4-isomer. It is not known whether achieving the 1,5-isomer selectively using ruthenium-based catalysts is possible on surfaces.…”

Section: Introductionmentioning

confidence: 99%

On-Surface Azide–Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?

Dief

Kalužná

et al. 2022

Langmuir

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Owing to its simplicity, selectivity, high yield, and the absence of byproducts, the “click” azide–alkyne reaction is widely used in many areas. The reaction is usually catalyzed by copper(I), which selectively produces the 1,4-disubstituted 1,2,3-triazole regioisomer. Ruthenium-based catalysts were later developed to selectively produce the opposite regioselectivity—the 1,5-disubstituted 1,2,3-triazole isomer. Ruthenium-based catalysis, however, remains only tested for click reactions in solution, and the suitability of ruthenium catalysts for surface-based click reactions remains unknown. Also unknown are the electrical properties of the 1,4- and 1,5-regioisomers, and to measure them, both isomers need to be assembled on the electrode surface. Here, we test whether ruthenium catalysts can be used to catalyze surface azide–alkyne reactions to produce 1,5-disubstituted 1,2,3-triazole, and compare their electrochemical properties, in terms of surface coverages and electron transfer kinetics, to those of the compound formed by copper catalysis, 1,4-disubstituted 1,2,3-triazole isomer. Results show that ruthenium(II) complexes catalyze the click reaction on surfaces yielding the 1,5-disubstituted isomer, but the rate of the reaction is remarkably slower than that of the copper-catalyzed reaction, and this is related to the size of the catalyst involved as an intermediate in the reaction. The electron transfer rate constant ( k et ) for the ruthenium-catalyzed reaction is 30% of that measured for the copper-catalyzed 1,4-isomer. The lower conductivity of the 1,5-isomer is confirmed by performing nonequilibrium Green’s function computations on relevant model systems. These findings demonstrate the feasibility of ruthenium-based catalysis of surface click reactions and point toward an electrical method for detecting the isomers of click reactions.

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Maximizing Conversion of Surface Click Reactions for Versatile Molecular Modification on Metal Oxide Nanowires

Cited by 6 publications

References 37 publications

Interfacial Molecular Compatibility for Programming Organic–Metal Oxide Superlattices

Interfacial Molecular Compatibility for Programming Organic–Metal Oxide Superlattices

Interfacial Molecular Compatibility for Programming Organic-Metal Oxide Superlattices

On-Surface Azide–Alkyne Cycloaddition Reaction: Does It Click with Ruthenium Catalysts?

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