Heterometallic Actinide‐Containing Photoresponsive Metal‐Organic Frameworks: Dynamic and Static Tuning of Electronic Properties

Abstract

Acquiring fundamental knowledge of properties of actinide‐based materials is a necessary step to create new possibilities for addressing the current challenges in the nuclear energy and nuclear waste sectors. In this report, we established a photophysics–electronics correlation for actinide‐containing metal‐organic frameworks (An‐MOFs) as a function of excitation wavelength, for the first time. A stepwise approach for dynamically modulating electronic properties was applied for the first time towards actinide‐based heterometallic MOFs through integration of photochromic linkers. Optical cycling, modeling of density of states near the Fermi edge, conductivity measurements, and photoisomerization kinetics were employed to shed light on the process of tailoring optoelectronic properties of An‐MOFs. Furthermore, the first photochromic MOF‐based field‐effect transistor, in which the field‐effect response could be changed through light exposure, was constructed. As a demonstration, the change in current upon light exposure was sufficient to operate a two‐LED fail‐safe indicator circuit.

Photoresponsive Metal-Organic Frameworks as Adjustable Scaffolds in Reticular Chemistry

“…metal-organic frameworks [76]. This work demonstrated that the electronic properties of these materials can be tuned by different approaches: (i) incorporation of photoswitches; (ii) integration of a secondary metal; (iii) inclusion of a guest inside the MOF pores.…”

“…The same research group also studied the tailoring and tunability of the optoelectronic properties of mono-and heterometallic actinide-containing spiropyran-based metal-organic frameworks [76]. This work demonstrated that the electronic properties of these materials can be tuned by different approaches: (i) incorporation of photoswitches; (ii) integration of a secondary metal; (iii) inclusion of a guest inside the MOF pores.…”

“…Favorable properties of these materials herald possible applications in other fields, such as Nanorobotics, Data Storage and Optoelectronics (Table 1, entries 5-7 and 9) [53,76,78,85,87].…”

“…Most of the currently implemented applications of these photoresponsive MOFs are at the research laboratory level. The spiropyran-based MOFs synthesized by Professor Shustova have been successfully used for the development of FET and LED devices (Table 1, entry 5) [76]. This technological application makes evident the importance of the incorporation of photocromic MOF scaffolds placed at a FET device in order to orthogonally control the drain current.…”

Photoresponsive Metal‐Organic Frameworks: Tailorable Platforms of Photoswitches for Advanced Functions

“…Great increase in the conductance was observed in the In another study, Shustova and co-workers reported an actinide-containing MOF which exhibited photophysics-electronics correlation. [80] The electronic properties of the heterometallic actinide-based MOF could be dynamically modulated by the integration of photochromic linkers. In particular, fieldeffect transistors were constructed based on the photochromic MOFs to realize changes in the field-effect response upon light exposure.…”