Improving LMOF luminescence quantum yield through guest-mediated rigidification

Luminescent metal-organic frameworks (LMOFs) are among the fastest growing solid-state optical materials and have been studied for a wide variety of applications. However, when developing a new LMOF, it can be challenging to balance a strong luminescence quantum yield with all other important proper...

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Bibliographic Details
Published in:Journal of materials chemistry. C, Materials for optical and electronic devices Materials for optical and electronic devices, 2019-11, Vol.7 (46), p.14739-14744
Main Authors: Lustig, William P, Teat, Simon J, Li, Jing
Format: Article
Language:English
Subjects:
Crystallography
Design modifications
Emission analysis
Emission spectra
Flexibility
Luminescence
Metal-organic frameworks
Optical materials
Organic chemistry
Single crystals
Thermogravimetric analysis
Toxicity
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Summary:Luminescent metal-organic frameworks (LMOFs) are among the fastest growing solid-state optical materials and have been studied for a wide variety of applications. However, when developing a new LMOF, it can be challenging to balance a strong luminescence quantum yield with all other important properties required by the intended application (appropriate excitation/emission wavelengths, chemical and physical stability, low toxicity, etc .). Being able to post-synthetically improve a LMOF's quantum yield is valuable, as it offers additional tunability in materials design and modification. As framework flexibility can limit quantum yield, post-synthetic methods of rigidifying an LMOF have the potential to improve its performance. This paper discusses a pair of nearly identical isoreticular LMOFs, and uses them as a model system to investigate how framework flexibility affects quantum yield. Introducing optically-inactive guests into a LMOF pore is shown to be an effective method for rigidifying the framework, improving the quantum yield of a flexible LMOF from 12.2% to 59.3%-an improvement of nearly 400%. Rotation of a specific pyridyl ring in LMOF-236 is locked by loading guest molecules into the MOF's pore, improving quantum yield by nearly 400%-an example of a generalizable strategy for maximizing quantum yield via guest-packing rigidification.
ISSN:2050-7526
2050-7534
DOI:10.1039/c9tc05216j