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Facile loading of thin-film surface-anchored metal-organic frameworks with Lewis-base guest molecules†
Materials Chemistry Frontiers ( IF 6.0 ) Pub Date : 2017-05-31 00:00:00 , DOI: 10.1039/c7qm00142h
Nicolò Baroni 1, 2, 3, 4 , Andrey Turshatov 1, 2, 3, 4 , Michael Oldenburg 1, 2, 3, 4 , Dmitry Busko 1, 2, 3, 4 , Michael Adams 1, 2, 3, 4 , Ritesh Haldar 2, 3, 4, 5 , Alexander Welle 2, 3, 4, 5 , Engelbert Redel 2, 3, 4, 5 , Christof Wöll 2, 3, 4, 5 , Bryce S. Richards 1, 2, 3, 4, 6 , Ian A. Howard 1, 2, 3, 4, 6
Affiliation  

In this work, we demonstrate how dye molecules with lone electron pairs, Lewis-base functionality, can be loaded into a surface anchored metal-organic framework system (SURMOF-2) directly from ethanolic solution without the need for any activation procedure. The dye loading profile throughout the SURMOF-2 layer is confirmed by time-of-flight secondary ion mass spectrometry (ToF-SIMS). The loaded porphyrin dyes show signs of aggregation, characterized by broadening of the absorption spectra and changes in the emission spectra and lifetimes. The triplet exciton dynamics of the Pd and Pt metallated porphyrin after inclusion in the SURMOF are characterized by a red-shifted phosphorescence (around 800 nm peak) with a lifetime in the range of 50 μs. The monomer-like emission (620 nm) has a lifetime of less than 3 μs. Similarly, the singlet dynamics of the Zn metallated porphyrin show no sign of residual monomer emission in the SURMOF. In summary, these results show a route through which guest molecules can be easily loaded into SURMOFs. The loading is achieved with a printing-compatible technique and it can lead to guest molecule concentrations that are sufficiently high that there are strong interactions between guest molecules. This opens interesting avenues towards printing guest molecules onto SURMOFs to selectively bestow new properties to patterned loaded areas of the SURMOF.

中文翻译:

带有路易斯碱的客体分子的薄膜表面锚定的金属-有机框架的容易装载

在这项工作中,我们演示了如何将含孤电子对的染料分子(基于Lewis的功能)直接从乙醇溶液中加载到表面锚定的金属有机骨架系统(SURMOF-2)中,而无需任何激活程序。通过飞行时间二次离子质谱(ToF-SIMS)确认了整个SURMOF-2层的染料负载情况。负载的卟啉染料表现出聚集迹象,其特征在于吸收光谱变宽以及发射光谱和寿命的变化。包含在SURMOF中后,Pd和Pt金属化的卟啉的三重态激子动力学特征是红移磷光(峰值约800 nm),寿命在50μs范围内。类单体发射(620 nm)的寿命小于3μs。相似地,锌金属化卟啉的单重态动力学表明在SURMOF中没有残留单体发射的迹象。总而言之,这些结果显示了一种途径,通过该途径,客体分子可以轻松地装载到SURMOF中。负载是通过与打印兼容的技术来实现的,并且可以导致来宾分子的浓度足够高,从而使来宾分子之间发生强烈的相互作用。这为将客体分子印刷到SURMOFs上开辟了有趣的途径,以选择性地赋予SURMOF图案化加载区域新的特性。负载是通过与打印兼容的技术来实现的,并且可以导致来宾分子的浓度足够高,从而使来宾分子之间发生强烈的相互作用。这为将客体分子印刷到SURMOFs上开辟了有趣的途径,以选择性地赋予SURMOF图案化加载区域新的特性。负载是通过与打印兼容的技术来实现的,并且可以导致来宾分子的浓度足够高,从而使来宾分子之间存在强烈的相互作用。这为将客体分子印刷到SURMOFs上开辟了有趣的途径,以选择性地赋予SURMOF图案化加载区域新的特性。
更新日期:2017-05-31
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