Cracking Down on Vapochromic Salts: Unveiling Vapomechanical Stress in Gas-Sorbing Platinum Complexes

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2024-11-15 DOI:10.1039/d4dt02053g

Amie E. Norton, Stephen Taylor, Caroline Williams, Ann Zoller, Watts Dietrich, William Connick, Sayandev Chatterjee

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Abstract

This study explores the vapochromic and vapoluminescent behaviors of [Pt(tpy)Cl]PF6 host molecules (tpy = 2,2':6',2''-terpyridine) under acetonitrile (CH3CN) vapor guest, challenging the conventional view that these phenomena arise solely from direct host-guest interactions. Our findings reveal a cooperative mechanism where mechanochromic surface perturbations prime the Pt(II) host for guest incorporation, leading to initial color and luminescence changes prior to significant structural alterations. While the color transition between the yellow [Pt(tpy)Cl]PF6 form and the red/orange [Pt(tpy)Cl]PF6•CH3CN form is reversible, repeated vapor cycling induces a loss of crystallinity, as indicated by diffraction peak broadening and emission shifts. Scanning electron microscopy analyses show mechanical deformations like bending and surface pitting, emphasizing the role of vapomechanical stress in altering optical properties. These insights highlight the need for integrated design strategies in developing robust vapochromic materials for gas sensing applications.

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破解汽相盐：揭示吸气铂络合物中的蒸汽机械应力

本研究探讨了[Pt(tyy)Cl]PF6 主分子（tyy = 2,2':6',2''-三联吡啶）在乙腈（CH3CN）蒸气客体作用下的蒸发变色和蒸发发光行为，对传统观点（即这些现象仅源于主-客体的直接相互作用）提出了挑战。我们的研究结果揭示了一种合作机制，在这种机制中，机械变色表面扰动为客体掺入铂(II)宿主提供了条件，从而在结构发生重大改变之前导致最初的颜色和发光变化。虽然黄色的 [Pt(tpy)Cl]PF6 形式和红色/橙色的 [Pt(tpy)Cl]PF6-CH3CN 形式之间的颜色转变是可逆的，但反复的蒸汽循环会导致结晶度下降，这一点可以从衍射峰扩大和发射偏移中看出。扫描电子显微镜分析显示了弯曲和表面点蚀等机械变形，强调了蒸汽机械应力在改变光学特性方面的作用。这些见解突出表明，在开发用于气体传感应用的坚固耐用的气致变色材料时，需要采用综合设计策略。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.