与 Ln(六氟乙酰丙酮)3 核心配位的基于 Terpyridyl-Imidazole 的配体:溶液和 PMMA 薄膜中的合成、结构表征、发光特性和热感应行为

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Toushique Ahmed, Amit Chakraborty and Sujoy Baitalik*, 
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引用次数: 0

摘要

合成了一系列新的三元镧系配合物,其形式为[Ln(hfa)3(tyy-HImzphen)],并对其进行了全面表征,其中 Ln = LaIII (1)、EuIII (2)、SmIII (3) 和 TbIII (4);hfa = 六氟乙酰丙酮;tyy-HImzphen = 2-(4-[2,2′:6′,2″]terpyridin-4′-yl-phenyl)-1H-phenanthro[9,10-d]imidazole.在 Ln-hfa 分子上掺入 tpy-HImzphen 会使配合物的吸收窗口向可见光区发生浴色偏移。为了了解复合物的失活途径,我们在 RT 和 77 K 条件下对发光特性进行了广泛的研究。稳态和时间分辨发射光谱行为都表明,在镧系元素核心掺入 tpy-HImzphen 后会出现四种不同的行为,即 LaIII 的配体中心峰会发生巨大的红移;EuIII 几乎完全发生了能量转移;SmIII 几乎没有发生能量转移,而 TbIII 则发生了反向能量转移。此外,EuIII 复合物在溶液状态和聚(甲基丙烯酸甲酯)(PMMA)薄膜中的发光测温中也表现出了卓越的性能。溶液中的热敏发光响应被进一步用于模拟设置-复位触发器的逻辑运算。我们设计了一种合理的能量转移方案来解释复合物中不同的发光行为。此外,还考虑了 LMCT 在 Eu(III) 复合物热感应特性中的作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Terpyridyl-Imidazole Based Ligand Coordinated to Ln(Hexafluoroacetyl acetonate)3 Core: Synthesis, Structural Characterization, Luminescence Properties, and Thermosensing Behaviors in Solution and PMMA Film

Terpyridyl-Imidazole Based Ligand Coordinated to Ln(Hexafluoroacetyl acetonate)3 Core: Synthesis, Structural Characterization, Luminescence Properties, and Thermosensing Behaviors in Solution and PMMA Film

Terpyridyl-Imidazole Based Ligand Coordinated to Ln(Hexafluoroacetyl acetonate)3 Core: Synthesis, Structural Characterization, Luminescence Properties, and Thermosensing Behaviors in Solution and PMMA Film

A new array of ternary lanthanide complexes of the form [Ln(hfa)3(tpy-HImzphen)] have been synthesized and thoroughly characterized wherein Ln = LaIII (1), EuIII (2), SmIII (3), and TbIII (4); hfa = hexafluoroacetylacetonate; and tpy-HImzphen = 2-(4-[2,2′:6′,2″]terpyridin-4′-yl-phenyl)-1H-phenanthro[9,10-d]imidazole. Incorporation of tpy-HImzphen onto the Ln-hfa moiety induced a bathochromic shift of the absorption window of the complexes into the visible region. Extensive investigations of the luminescence characteristics have been conducted both at RT and at 77 K to understand the deactivation pathways of the complexes. Both steady-state and time-resolved emission spectral behaviors indicate four distinctive behaviors upon incorporation of tpy-HImzphen onto the lanthanide core, viz., a huge red-shift of the ligand-centered peak for LaIII; almost complete energy transfer for EuIII; very little energy transfer for SmIII, while reverse energy transfer in the case of TbIII. In addition, the EuIII-complex exhibits its excellence in luminescence thermometry in the solution state as well as in poly(methyl methacrylate) (PMMA) thin films. The thermosensitive luminescence response in solution was further utilized to mimic set–reset flip-flop logic operation. A plausible energy transfer scheme has been devised to explain dissimilar luminescence behaviors in the complexes. The role of LMCT was also considered for the observed thermosensing property of the Eu(III) complex.

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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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