Thermoresponse of Odd-Even Effect in n-Alkanethiolate Self-Assembled Monolayers on Gold Substrates**

Sohyun Park; Eunchan Kim; Youngjin Choi; Jiung Jang; Kyungwon Kwak; Minhaeng Cho; Hyo Jae Yoon

doi:10.1002/chem.202203536

Thermoresponse of Odd-Even Effect in n-Alkanethiolate Self-Assembled Monolayers on Gold Substrates**

Sohyun Park, Eunchan Kim, Youngjin Choi, Jiung Jang, Kyungwon Kwak, Minhaeng Cho, Hyo Jae Yoon

Department of Chemistry

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

3 Citations (Scopus)

Abstract

This study examines thermoresponse of odd-even effect in self-assembled monolayers (SAMs) of n-alkanethiolates (SC_n, n=3–18) formed on template-stripped gold (Au^TS) using macro- and microscopic analytical techniques, contact angle goniometry (CAG) and vibrational sum frequency generation (VSFG) spectroscopy, respectively. Both CAG and VSFG analyses showed that the odd-even effect in liquid-like SAMs (n=3–9) disappeared upon heating at 50–70 °C, indicating that the heating led to increased structural disorder regardless of odd and even carbon numbers. In contrast, the opposite thermoresponse was observed for odd and even SC_n molecules in wax- and solid-like SAMs (n=10–18). Namely, temperature-dependent orientational change of terminal CH₃ relative to the surface normal was opposite for the odd and even molecules, thereby leading to mitigated odd-even effect. Our work offers important insights into thermoresponse of supramolecular structure in condensed organic matter.

Original language	English
Article number	e202203536
Journal	Chemistry - A European Journal
Volume	29
Issue number	15
DOIs	https://doi.org/10.1002/chem.202203536
Publication status	Published - 2023 Mar 13

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation of Korea (NRF‐2019R1A6A1A11044070; NRF‐2019R1A2C2011003; NRF‐2021M3F3A2A03017999 for H.J.Y, and NRF‐2020R1A2C2010675; NRF‐2020R1A5A1019141 for K.K.) and IBS‐R023‐D1 (M.C.). S.P. acknowledges the support of the POSCO TJ Park Doctoral Fellowship.

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

Keywords

contact angle goniometry
heat
odd-even effects
self-assembled monolayers
sum-frequency-generation spectroscopy

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.202203536

Cite this

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title = "Thermoresponse of Odd-Even Effect in n-Alkanethiolate Self-Assembled Monolayers on Gold Substrates**",

abstract = "This study examines thermoresponse of odd-even effect in self-assembled monolayers (SAMs) of n-alkanethiolates (SCn, n=3–18) formed on template-stripped gold (AuTS) using macro- and microscopic analytical techniques, contact angle goniometry (CAG) and vibrational sum frequency generation (VSFG) spectroscopy, respectively. Both CAG and VSFG analyses showed that the odd-even effect in liquid-like SAMs (n=3–9) disappeared upon heating at 50–70 °C, indicating that the heating led to increased structural disorder regardless of odd and even carbon numbers. In contrast, the opposite thermoresponse was observed for odd and even SCn molecules in wax- and solid-like SAMs (n=10–18). Namely, temperature-dependent orientational change of terminal CH3 relative to the surface normal was opposite for the odd and even molecules, thereby leading to mitigated odd-even effect. Our work offers important insights into thermoresponse of supramolecular structure in condensed organic matter.",

keywords = "contact angle goniometry, heat, odd-even effects, self-assembled monolayers, sum-frequency-generation spectroscopy",

author = "Sohyun Park and Eunchan Kim and Youngjin Choi and Jiung Jang and Kyungwon Kwak and Minhaeng Cho and Yoon, {Hyo Jae}",

note = "Funding Information: This work was supported by the National Research Foundation of Korea (NRF‐2019R1A6A1A11044070; NRF‐2019R1A2C2011003; NRF‐2021M3F3A2A03017999 for H.J.Y, and NRF‐2020R1A2C2010675; NRF‐2020R1A5A1019141 for K.K.) and IBS‐R023‐D1 (M.C.). S.P. acknowledges the support of the POSCO TJ Park Doctoral Fellowship. Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

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AU - Park, Sohyun

AU - Kim, Eunchan

AU - Choi, Youngjin

AU - Jang, Jiung

AU - Kwak, Kyungwon

AU - Cho, Minhaeng

AU - Yoon, Hyo Jae

N1 - Funding Information: This work was supported by the National Research Foundation of Korea (NRF‐2019R1A6A1A11044070; NRF‐2019R1A2C2011003; NRF‐2021M3F3A2A03017999 for H.J.Y, and NRF‐2020R1A2C2010675; NRF‐2020R1A5A1019141 for K.K.) and IBS‐R023‐D1 (M.C.). S.P. acknowledges the support of the POSCO TJ Park Doctoral Fellowship. Publisher Copyright: © 2022 Wiley-VCH GmbH.

PY - 2023/3/13

Y1 - 2023/3/13

N2 - This study examines thermoresponse of odd-even effect in self-assembled monolayers (SAMs) of n-alkanethiolates (SCn, n=3–18) formed on template-stripped gold (AuTS) using macro- and microscopic analytical techniques, contact angle goniometry (CAG) and vibrational sum frequency generation (VSFG) spectroscopy, respectively. Both CAG and VSFG analyses showed that the odd-even effect in liquid-like SAMs (n=3–9) disappeared upon heating at 50–70 °C, indicating that the heating led to increased structural disorder regardless of odd and even carbon numbers. In contrast, the opposite thermoresponse was observed for odd and even SCn molecules in wax- and solid-like SAMs (n=10–18). Namely, temperature-dependent orientational change of terminal CH3 relative to the surface normal was opposite for the odd and even molecules, thereby leading to mitigated odd-even effect. Our work offers important insights into thermoresponse of supramolecular structure in condensed organic matter.

AB - This study examines thermoresponse of odd-even effect in self-assembled monolayers (SAMs) of n-alkanethiolates (SCn, n=3–18) formed on template-stripped gold (AuTS) using macro- and microscopic analytical techniques, contact angle goniometry (CAG) and vibrational sum frequency generation (VSFG) spectroscopy, respectively. Both CAG and VSFG analyses showed that the odd-even effect in liquid-like SAMs (n=3–9) disappeared upon heating at 50–70 °C, indicating that the heating led to increased structural disorder regardless of odd and even carbon numbers. In contrast, the opposite thermoresponse was observed for odd and even SCn molecules in wax- and solid-like SAMs (n=10–18). Namely, temperature-dependent orientational change of terminal CH3 relative to the surface normal was opposite for the odd and even molecules, thereby leading to mitigated odd-even effect. Our work offers important insights into thermoresponse of supramolecular structure in condensed organic matter.

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Thermoresponse of Odd-Even Effect in n-Alkanethiolate Self-Assembled Monolayers on Gold Substrates**

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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