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Integration of Fluorescent Functionality into Pressure Amplifying Metal-Organic Frameworks

preprint
submitted on 26.05.2021, 12:12 and posted on 27.05.2021, 06:42 by Francesco Walenszus, Jack D. Evans, Volodymyr Bon, Friedrich Schwotzer, Irena Senkovska, Stefan Kaskel
The flexibility of soft porous crystals, i.e., their ability to respond to external stimuli with structural changes, is one of the most fascinating features of metal-organic frameworks. In addition to breathing and swelling phenomena of flexible MOFs, negative gas adsorption and pressure amplification is one of the more recent discoveries in this field, initially observed in the cubic DUT-49 framework. In recent years the structural contraction was monitored by physisorption, X‑ray diffraction, NMR and EPR techniques, providing only limited information about the electronic structure of the ligand. In this work we designed a new ligand with a fluorescent core in the linker backbone and synthesized three new MOFs, isoreticular to DUT-49, denoted as DUT‑140(M) (M - Cu, Co, Zn) crystalizing in space group. DUT‑140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m2g-1 and a pore volume of 2.59 cm3g-1. Furthermore, it shows flexibility and NGA upon adsorption of subcritical gases. DUT-140(Zn), synthesized using post-synthetic metal exchange, could only be studied with guests in the pores. In addition to the investigation of the adsorption behavior of DUT-140(Cu) spectroscopic and computational methods were used to study the light absorption properties.

Funding

ERC advanced grant amplipore No 742743

BMBF Project No 05K19OD2

DFG/ANR Project No 391704421

History

Email Address of Submitting Author

volodymyr.bon@tu-dresden.de

Institution

Technische Universität Dresden

Country

Deutschland

ORCID For Submitting Author

0000-0002-9851-5031

Declaration of Conflict of Interest

We declare no conflict of interests

Version Notes

version 1.0