One-way photoisomerization of ligands for permanent switching of metal complexes

Lvov, Andrey G.; Mörtel, Max; Heinemann, Frank W.; Khusniyarov, Marat M.

doi:10.1039/d1tc00761k

Cited by 7 publications

(14 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In particular, the occurrence of a side-reaction that transforms the closed isomer 1c into an annulated bis(dihydro-thiopyran) side-product ( 9 in Figure b) could be confirmed by 1 H NMR spectroscopy (Figure ). Furthermore, this species, which is a well-known source of fatigue within dithienylethene-type molecular switches, − could be isolated and characterized (Section S3 in the SI). Although the side-reaction clearly hampers the reversible photoswitching of 1 , the process is not fully inhibited (Figures a and S7 and S8 in the SI).…”

Section: Resultsmentioning

confidence: 99%

Photoswitching of Local (Anti)Aromaticity in Biphenylene-Based Diarylethene Molecular Switches

et al. 2022

View full text Add to dashboard Cite

Photoinduced tuning of (anti)aromaticity and associated molecular properties is currently in the focus of attention for both tailoring photochemical reactivity and designing new materials. Here, we report on the synthesis and spectroscopic characterization of diarylethene-based molecular switches embedded in a biphenylene structure composed of rings with different levels of local (anti)aromaticity. We show that it is possible to modulate and control the (anti)aromatic character of each ring through reversible photoswitching of the aryl units of the system between open and closed forms. Remarkably, it is shown that the irreversible formation of an annulated bis(dihydro-thiopyran) side-product that hampers the photoswitching can be efficiently suppressed when the aryl core formed by thienyl groups in one switch is replaced by thiazolyl groups in another.

show abstract

Section: Resultsmentioning

confidence: 99%

Photoswitching of Local (Anti)Aromaticity in Biphenylene-Based Diarylethene Molecular Switches

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Firstly, photolysis should be performed in the absence of oxygen to protect the substrate, the key intermediate DAE‐c, and the product from harmful photogenerated oxygen species, first of all, singlet oxygen [53] . For example, in the synthesis of 11 a under aerobic conditions, we observed a significant amount of decomposition products as a yellowish brown powder [49] . High‐energy UV light is yet another potential source of side reactions.…”

Section: Scope Of the Photorearrangementmentioning

confidence: 98%

“…In fact, full conversion of the initial diarylethene was reached after 45 h and 98 h for 10 a and 11 a , respectively. To boost the photoreaction, two light sources (313 and 365 nm) were used simultaneously in the syntheses of 4 a and 11 a [43,49] . The effect is based on the selective action of UV (365 nm) on the intermediate DAE‐c , which is possible due to the much stronger absorption of DAE‐c at 350–400 nm in comparison with DAE‐o .…”

Section: Scope Of the Photorearrangementmentioning

confidence: 99%

“…The molecular structures of six DDA dyes were studied by X‐ray crystallography (Figure 3). [6,40,46,48–50] The two central carbon atoms have tetrahedral configuration in accordance with their sp 3 ‐hybridization. The methyl groups are arranged in opposite directions, which allows the chromophore to retain its overall planarity.…”

Section: Structure Of Dda Dyesmentioning

confidence: 99%

“…The redox properties of DDA dyes 3‐a [42] and 11‐a [49] were studied by cyclic voltammetry (Figure 4). Dye 3 a displayed a reversible one‐electron oxidation wave with E ox =0.45 V vs Ag/Ag + in CH 3 CN containing 0.1 M Et 4 NClO 4 .…”

Section: Properties Of Dda Dyesmentioning

confidence: 99%

See 2 more Smart Citations

Light‐Induced Dyotropic Rearrangement of Diarylethenes: Scope, Mechanism, and Prospects

Lvov

Kouame

Khusniyarov

2023

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Irreversible two‐photon photorearrangement of 1,2‐diarylethenes is a unique process providing access to complex 2a1,5a‐dihydro‐5,6‐dithiaacenaphthylene (DDA) heterocyclic core. This reaction was serendipitously discovered during studies on photoswitchable diarylethenes and was initially considered as a highly undesired process. However, in recent years, it has been recognized as an efficient photochemical reaction, interesting by itself and as a promising synthetic method for the synthesis of challenging molecules. Herein, we discuss the state‐of‐the‐art in studies on this notable process.

show abstract

Synthesis and Development of Inverse‐Type Nucleoside Diarylethene Photoswitches

Hendrich,

Reinschmidt,

Büllmann

et al. 2024

Chemistry A European J

View full text Add to dashboard Cite

Nucleosidic diarylethenes (DAEs) have evolved from an emerging class of photochromes into a well‐established option for integrating photochromic functionalities into biological systems. However, a comprehensive understanding of how chemical structure influences their photochromic properties remains essential. While structural features, such as an inverse connection between the aryl residues and the ethene bridge, are well‐documented for classical DAEs, their application to nucleosidic DAEs has been underexplored. In this study, we address this gap by developing three distinct types of inverse nucleosidic DAEs – semi‐inverse thiophenes, semi‐inverse uridines and inverse uridines. We successfully synthesized these compounds and conducted comprehensive analyses of their photostationary states, thermal stability, reversibility, and reaction quantum yields. Additionally, we conducted an in‐depth comparison of their photochromic properties with those of their normal‐type counterparts. Among the synthesized compounds, seven semi‐inverse thiophenes exhibited the most promising characteristics. Notably, these compounds demonstrated excellent fatigue resistance, with up to 96% retention of photochromic activity over 40 switching cycles, surpassing the performance of all comparable nucleosidic DAEs reported to date. These findings hold significant promise for future applications in various fields.

show abstract

One-way photoisomerization of ligands for permanent switching of metal complexes

Abstract: One-way photoisomerization of ligands within metal complexes is a nearly unknown phenomenon. We disclosed that a diarylethene-based ligand L-o undergoes quantitative irreversible photoisomerization to a photo- and thermostable annulated isomer...

Cited by 7 publications

References 57 publications

Photoswitching of Local (Anti)Aromaticity in Biphenylene-Based Diarylethene Molecular Switches

Photoswitching of Local (Anti)Aromaticity in Biphenylene-Based Diarylethene Molecular Switches

Light‐Induced Dyotropic Rearrangement of Diarylethenes: Scope, Mechanism, and Prospects

Synthesis and Development of Inverse‐Type Nucleoside Diarylethene Photoswitches

Contact Info

Product

Resources

About