Thermoresponsive Platinum(II) 2,6-Di(pyrid-2-yl)pyrazine Complexes with Unusual Aggregation Behavior upon Heating.

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Tracy Ho-Ying Chan, Ziyong Chen, Ming-Yi Leung, Michael Ho-Yeung Chan, Eric Ka-Ho Wong, Wai Kit Tang, Vivian Wing-Wah Yam
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引用次数: 0

Abstract

A series of alkynylplatinum(II) complexes with 2,6-di(pyrid-2-yl)pyrazine ligand has been synthesized and characterized. Interestingly, the complexes have been found to exhibit unprecedented thermochromic behavior with absorption maxima shifting to the longer-wavelength region upon increasing temperature. This phenomenon is significantly different from that in conventional platinum(II) systems, where an elevated temperature typically promotes the dissociation of aggregates and diminishes MMLCT absorptions. Transmission electron microscopy (TEM) and variable-temperature 1H NMR spectroscopy suggest a thermoresponsive morphological transformation behavior from rods to circular morphologies, driven by the preferential formation of π-π and Pt···Pt interactions over hydrogen bonding interactions upon the disruption of hydrogen bonding at high temperature, as supported by solution-state Fourier transform infrared (FT-IR) spectroscopy together with computational studies. This unusual optical and morphological transformation is rarely observed, as it represents a stark contrast to the deaggregation behavior upon increasing temperature typical of the control and commonly found platinum(II) complexes and organic compounds.

热响应性铂(II) 2,6-二(吡啶-2-基)吡嗪配合物在加热时异常聚集行为。
合成了一系列以2,6-二(吡啶-2-基)吡嗪为配体的炔基铂配合物,并对其进行了表征。有趣的是,这些配合物表现出前所未有的热致变色行为,随着温度的升高,吸收最大值向更长的波长区域移动。这种现象与传统铂(II)体系明显不同,在传统铂(II)体系中,升高的温度通常会促进聚集体的解离,并减少MMLCT的吸收。透射电子显微镜(TEM)和变温1H NMR谱分析表明,高温氢键破坏时,π-π和Pt··Pt相互作用优先于氢键相互作用,从而导致了从棒状到圆形的热响应性形态转变行为,溶液态傅里叶变换红外光谱(FT-IR)和计算研究支持了这一结果。这种不寻常的光学和形态转变很少被观察到,因为它与典型的控制和常见的铂(II)配合物和有机化合物的温度升高时的解聚行为形成鲜明对比。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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