This paper 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.

中文翻译：

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自组装单层膜中奇偶效应的热响应

本文研究了使用宏观和微观分析技术、接触角测角法在模板剥离金 (AuTS) 上形成的正硫醇盐 (SCn, n = 3 – 18) 自组装单分子层 (SAM) 中奇偶效应的热响应（CAG）和振动和频产生（VSFG）光谱，分别。CAG 和 VSFG 分析均表明，在 50 – 70 °C 加热时，液体状 SAM (n = 3 – 9) 中的奇偶效应消失，表明加热导致结构无序增加，无论奇数和偶数碳数如何. 相反，对于蜡状和固体状 SAM 中的奇数和偶数 SCn 分子（n = 10 – 18），观察到相反的热响应。即，末端CH3相对于表面法线的温度依赖性取向变化对于奇数和偶数分子是相反的，从而减轻奇偶效应。我们的工作为凝聚态有机物中超分子结构的热响应提供了重要的见解。