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

被引:27
作者
Halder, Arjun [1 ]
Bain, David C. [1 ]
Oktawiec, Julia [2 ]
Addicoat, Matthew A. [3 ]
Tsangari, Stavrini [1 ]
-Rivera, Jose J. Fuentes [1 ]
Pitt, Tristan A. [1 ]
Musser, Andrew J. [1 ]
Milner, Phillip J. [1 ]
机构
[1] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14850 USA
[2] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
[3] Nottingham Trent Univ, Sch Sci & Technol, Nottingham NG11 8NS, England
基金
美国国家卫生研究院; 美国国家科学基金会;
关键词
UNIVERSAL FORCE-FIELD; MOFS; LUMINESCENCE; FLUORESCENCE; EXTENSION; POROSITY; EXCITON; UIO-66; ACID; DYE;
D O I
10.1021/jacs.2c10672
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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 (TCPE4-) that exhibit an unex-pected 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.
引用
收藏
页码:1072 / 1082
页数:11
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