Synthesis, spectroscopic characterization, and photophysical properties of new p-anisolylthiol-functionalized platinum(II) bis(alkenylarylalkynyl) complexes

IF 1.6 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Transition Metal Chemistry Pub Date : 2023-08-16 DOI:10.1007/s11243-023-00550-x

Md. Mostafizur Rahman, Tanjila Islam, Md. Amran-Al-Taz Khan, Muhammad Younus, Dababrata Paul, Md. Sajib Joardar, Akiya Ogawa

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Abstract

A series of organic sulfur-functionalized trans-platinum(II) bis(alkenylarylalkynyl) complexes, having one anisolylthio group with general formula trans-[(PEt₃)₂Pt{C≡C–Ar–CH=CH(SC₆H₄–OCH₃)}₂], (2a-2d), (Ar = phenylene/biphenylene/2,5-dimethylphenylene/2,5-dimethoxyphenylene) was synthesized in excellent yields. All the new platinum(II) complexes have been fully characterized by physico-chemical and spectroscopic methods. Photophysical properties of the complexes were studied by absorption and emission spectroscopy. The lowest energy absorption band for the complexes, in the UV/Vis spectra, in THF solution, at room temperature, 2a-2d was observed in the range 355–391 nm, which depend on the spacers in the acetylide ligand e.g., the absorption of 2d is red shifted to 391 nm for the donor (OCH₃) substituents in phenyl spacer. These absorptions originated predominantly from π–π*orbitals of acetylide ligand with significant contribution from the platinum dπ orbital as evident from the HOMO and LUMO, obtained from TD-DFT calculations. Fluorescence was observed in all complexes at room temperature in the range 400–428 nm with PLQY of 2–5%. At 77 k, the complexes 2a-2b only exhibited phosphorescence in the range 579–585 nm, but there is no phosphorescence at ambient temperature.

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新型对苯硫基官能化铂（II）双（烯基芳基）配合物的合成、光谱表征和光物理性质

一系列有机硫官能化的反式铂（II）双（烯基芳基）配合物，具有一个通式为反式-[（PEt3）2Pt{C Select C–Ar–CH=CH（SC6H4–OCH3）}2]，（2a-2d），（Ar = 亚苯基/联苯/2，5-二甲基亚苯基/2，5-二甲氧基亚苯基）。所有新的铂（II）配合物都用物理化学和光谱方法进行了充分的表征。用吸收光谱和发射光谱研究了配合物的光物理性质。在室温下，在THF溶液中的UV/Vis光谱中，观察到配合物的最低能量吸收带2a-2d在355–391 nm范围内，这取决于乙酰基配体中的间隔物，例如，苯基间隔物中供体（OCH3）取代基的2d吸收红移到391 nm。这些吸收主要来自乙酰基配体的π–π*轨道，铂dπ轨道的显著贡献，从TD-DFT计算获得的HOMO和LUMO中可以明显看出。在室温下，在所有复合物中观察到荧光，范围为400–428 nm，PLQY为2–5%。在77k下，配合物2a-2b仅在579–585 nm范围内表现出磷光，但在环境温度下没有磷光。图形摘要

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来源期刊

Transition Metal Chemistry 化学-无机化学与核化学

CiteScore

3.60

自引率

0.00%

发文量

审稿时长

1.3 months

期刊介绍： Transition Metal Chemistry is an international journal designed to deal with all aspects of the subject embodied in the title: the preparation of transition metal-based molecular compounds of all kinds (including complexes of the Group 12 elements), their structural, physical, kinetic, catalytic and biological properties, their use in chemical synthesis as well as their application in the widest context, their role in naturally occurring systems etc. Manuscripts submitted to the journal should be of broad appeal to the readership and for this reason, papers which are confined to more specialised studies such as the measurement of solution phase equilibria or thermal decomposition studies, or papers which include extensive material on f-block elements, or papers dealing with non-molecular materials, will not normally be considered for publication. Work describing new ligands or coordination geometries must provide sufficient evidence for the confident assignment of structural formulae; this will usually take the form of one or more X-ray crystal structures.