TY - JOUR
T1 - Thermoresponse of Odd-Even Effect in n-Alkanethiolate Self-Assembled Monolayers on Gold Substrates**
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.
KW - contact angle goniometry
KW - heat
KW - odd-even effects
KW - self-assembled monolayers
KW - sum-frequency-generation spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85147776248&partnerID=8YFLogxK
U2 - 10.1002/chem.202203536
DO - 10.1002/chem.202203536
M3 - Article
C2 - 36548089
AN - SCOPUS:85147776248
SN - 0947-6539
VL - 29
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 15
M1 - e202203536
ER -