<br>通过缺陷工程增强金属有机框架中的动态光谱扩散,Journal of the American Chemical Society

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通过缺陷工程增强金属有机框架中的动态光谱扩散
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-03 , DOI: 10.1021/jacs.2c10672
Arjun Halder ₁ , David C Bain ₁ , Julia Oktawiec ₂ , Matthew A Addicoat ₃ , Stavrini Tsangari ₁ , José J Fuentes-Rivera ₁ , Tristan A Pitt ₁ , Andrew J Musser ₁ , Phillip J Milner ₁

Affiliation

有机发色团的晶体堆积对其光物理性质具有深远的影响。分子晶体工程通常无法生产用于光伏、发光二极管和传感器的精确间隔的分子阵列。一种有前途的替代策略是将发色团纳入晶体金属有机框架（MOF）中，从而在限制时产生基质配位诱导发射（MCIE）。然而，目前尚不清楚发色团和缺陷的精确排列如何决定这些系统中的光物理性质，从而限制了明确的光致发光材料的合理设计。在此，我们报告了由连接体四（4-羧基苯基）乙烯（TCPE ^4– ）构建的新型、坚固的基于Zr的MOF，其表现出意想不到的结构转变以及从绿色到蓝色光致发光（PL）的显着转变作为函数合成过程中使用的酸调节剂（苯甲酸、甲酸或乙酸）的量。时间分辨 PL (TRPL) 测量提供了完整的光谱信息，并揭示了观察到的低变色位移是由于在较高调制剂浓度下较高浓度的连接基取代缺陷而产生的，从而导致更广泛的激发转移引起的光谱扩散。迄今为止，这种类型的光谱扩散尚未在 MOF 中报道，其观察提供了使用传统晶体学技术无法获得的结构信息。我们的研究结果表明，缺陷对 MOF 的光物理性质具有深远的影响，并且可以轻松调整缺陷的存在以改变这些材料内的能量转移过程。

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Enhancing Dynamic Spectral Diffusion in Metal–Organic Frameworks through Defect Engineering

The crystal packing of organic chromophores has a profound impact on their photophysical properties. Molecular crystal engineering is generally incapable of producing precisely spaced arrays of molecules for use in photovoltaics, light-emitting diodes, and sensors. A promising alternative strategy is the incorporation of chromophores into crystalline metal–organic frameworks (MOFs), leading to matrix coordination-induced emission (MCIE) upon confinement. However, it remains unclear how the precise arrangement of chromophores and defects dictates photophysical properties in these systems, limiting the rational design of well-defined photoluminescent materials. Herein, we report new, robust Zr-based MOFs constructed from the linker tetrakis(4-carboxyphenyl)ethylene (TCPE^4–) that exhibit an unexpected structural transition in combination with a prominent shift from green to blue photoluminescence (PL) as a function of the amount of acid modulator (benzoic, formic, or acetic acid) used during synthesis. Time-resolved PL (TRPL) measurements provide full spectral information and reveal that the observed hypsochromic shift arises due to a higher concentration of linker substitution defects at higher modulator concentrations, leading to broader excitation transfer-induced spectral diffusion. Spectral diffusion of this type has not been reported in a MOF to date, and its observation provides structural information that is otherwise unobtainable using traditional crystallographic techniques. Our findings suggest that defects have a profound impact on the photophysical properties of MOFs and that their presence can be readily tuned to modify energy transfer processes within these materials.

更新日期：2023-01-03

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