0000000001313850
AUTHOR
Stefan Hecht
N,N′-Disubstituted Indigos as Readily Available Red-Light Photoswitches with Tunable Thermal Half-Lives
Some rare indigo derivatives have been known for a long time to be photochromic upon irradiation with red light, which should be advantageous for many applications. However, the absence of strategies to tune their thermal half-lives by modular molecular design as well as the lack of proper synthetic methods to prepare a variety of such molecules from the parent indigo dye have so far precluded their use. In this work, several synthetic protocols for N-functionalization have been developed, and a variety of N-alkyl and N-aryl indigo derivatives have been prepared. By installation of electron-withdrawing substituents on the N-aryl moieties, the thermal stability of the Z-isomers could be enha…
Reversible and Efficient Light-Induced Molecular Switching on an Insulator Surface
Prototypical molecular switches such as azobenzenes exhibit two states, i.e., trans and cis, with different characteristic physical properties. In recent years various derivatives were investigated on metallic surfaces. However, bulk insulators as supporting substrate reveal important advantages since they allow electronic decoupling from the environment, which is key to control the switching properties. Here, we report on the light-induced isomerization of an azobenzene derivative on a bulk insulator surface, in this case calcite (101̅4), studied by atomic force microscopy with submolecular resolution. Surprisingly, cis isomers appear on the surface already directly after preparation, indi…
Lichtaktivierte Sensoren zur empfindlichen Amindetektion
Unsere neue, einfache und akkurate colorimetrische Methode basiert auf Diarylethenen (DAEs) zur schnellen Detektion einer grosen Vielfalt primarer und sekundarer Amine. Die Sensoren bestehen aus aldehyd- oder ketonsubstituierten Diarylethenen, die selektiv ausgehend vom geschlossenen Isomer eine amininduzierte Entfarbungsreaktion eingehen. Somit konnen diese Sensoren zum gewunschten Zeitpunkt durch Lichteinstrahlung aktiviert werden und erlauben eine Empfindlichkeit der Amindetektion bis hinab zu 10−6 m in Losung. Zusatzlich ermoglicht die Immobilisierung auf Papier den Nachweis biogener Amine wie Cadaverin in der Gasphase oberhalb eines Grenzwerts von 12 ppbv innerhalb von 30 Sekunden.
Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes.
Upon light-induced isomerization, diarylethenes (DAEs) equipped with reactive aldehyde moieties rearrange selectively in the presence of amines, accompanied by decoloration. In a comprehensive study, the probe structure was optimized with regard to its inherent reactivity in the nucleophile-triggered rearrangement reaction. Detailed structure−reactivity relationships could be derived, in particular with regard to the type of integrated (het)aryl moieties as well as the location of the formyl residue, and the probes’ intrinsic reactivity with primary and secondary amines was optimized. Utilizing an ancillary base, the initially formed rearrangement product can engage in a subsequent catalyti…
Fluvial activity of the late-glacial to Holocene “Bergstraßenneckar” in the Upper Rhine Graben near Heidelberg, Germany – first results
Abstract. The term “Bergstraßenneckar” (BSN) refers to an abandoned course of the river Neckar. It flowed in a northern direction east of the river Rhine in the eastern part of the northern Upper Rhine Graben in southwestern Germany. The former meandering course merged with the Rhine ca. 50 km further north of the site of the present-day confluence near Mannheim. The palaeo-channels are still traceable by their depressional topography, in satellite images and by the curved boundaries of adjacent settlements and land parcels. In the plan view, satellite and aerial images reveal a succession of meander bends, with older bends being cut off from younger channels. Based on stratigraphic investi…
Protonenvermittelter Ringschluss eines negativ photochromen, Azulen‐basierten Diarylethens
Auf Protonen ansprechende photochrome Moleküle sind aufgrund ihrer Fähigkeit, auf nicht-invasive schnelle optische Stimuli zu reagieren, und wegen der ubiquitären Bedeutung von Protonierungs- und Deprotonierungsprozessen, sehr interessant. Üblicherweise befinden sich die sauren/basischen Stellen dieser Moleküle an Heteroatomen, die orthogonal zum photoaktiven π-Zentrum ausgerichtet sind. In dieser Arbeit wird Azulen, ein protonensensitiver reiner Kohlenwasserstoff, in das Gerüst eines Diarylethen-Photoschalters eingebaut. Dieser zeigt einen bisher ungekannten, protonenvermittelten, negativ photochromen Ringschluss. Veränderungen seiner optischen Eigenschaften durch Protonierung, sowohl in d…
Light-Activated Sensitive Probes for Amine Detection
Our new, simple, and accurate colorimetric method is based on diarylethenes (DAEs) for the rapid detection of a wide range of primary and secondary amines. The probes consist of aldehyde- or ketone-substituted diarylethenes, which undergo an amine-induced decoloration reaction, selectively to give the ring-closed isomer. Thus, these probes can be activated at the desired moment by light irradiation, with a sensitivity that allows the detection of amines at concentrations as low as 10exp−6 M in solution. In addition, the practical immobilization of DAEs on paper makes it possible to detect biogenic amines, such as cadaverine, in the gas phase above a threshold of 12 ppbv within 30 seconds. P…
Tuning of the electronic and photophysical properties of ladder-type quaterphenyl by selective methylene-bridge fluorination
The photophysics (spectral positions, band shapes, fluorescence quantum yields and lifetimes) of a series of fluorinated ladder type quaterphenyls L4P and L4P-Fn (n = 2, 4, 6) depend strongly on the degree and position of fluorine, despite the fact that substitution is not performed in the rings but only in methylene-bridges. This is driven by subtle differences in the molecular orbitals (MOs) participating in the electronic transitions, and in the vibronic pattern of the S0 and S1 electronic states as revealed by (TD)DFT calculations. Solid state spectra for n = 0, 2, 4 are similar to those of solution due to small intermolecular interactions as revealed by combined X-ray and (TD)DFT analy…
Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene
Abstract Proton‐responsive photochromic molecules are attractive for their ability to react on non‐invasive rapid optical stimuli and the importance of protonation/deprotonation processes in various fields. Conventionally, their acidic/basic sites are on hetero‐atoms, which are orthogonal to the photo‐active π‐center. Here, we incorporate azulene, an acid‐sensitive pure hydrocarbon, into the skeleton of a diarylethene‐type photoswitch. The latter exhibits a novel proton‐gated negative photochromic ring‐closure and its optical response upon protonation in both open and closed forms is much more pronounced than those of diarylethene photoswitches with hetero‐atom based acidic/basic moieties. …
Modulating the luminance of organic light-emitting diodes via optical stimulation of a photochromic molecular monolayer at transparent oxide electrode
Nanoscale 12(9), 5444-5451 (2020). doi:10.1039/D0NR00724B
Light-controlled reversible modulation of frontier molecular orbital energy levels in trifluoromethylated diarylethenes
Among bistable photochromic molecules, diarylethenes (DAEs) possess the distinct feature that upon photoisomerization they undergo a large modulation of their π-electronic system, accompanied by a marked shift of the HOMO/LUMO energies and hence oxidation/reduction potentials. The electronic modulation can be utilized to remote-control charge- as well as energy-transfer processes and it can be transduced to functional entities adjacent to the DAE core, thereby regulating their properties. In order to exploit such photoswitchable systems it is important to precisely adjust the absolute position of their HOMO and LUMO levels and to maximize the extent of the photoinduced shifts of these energ…
Diarylethenes in Optically Switchable Organic Light-Emitting Diodes: Direct Investigation of the Reversible Charge Carrier Trapping Process
Advanced optical materials 10, (2021). doi:10.1002/adom.202101116
CCDC 1508362: Experimental Crystal Structure Determination
Related Article: Virginia Valderrey, Aurelio Bonasera, Sebastian Fredrich, Stefan Hecht|2017|Angew.Chem.,Int.Ed.|56|1914|doi:10.1002/anie.201609989
CCDC 1518489: Experimental Crystal Structure Determination
Related Article: Martin Herder, Fabian Eisenreich, Aurelio Bonasera, Anna Grafl, Lutz Grubert, Michael Pätzel, Jutta Schwarz, Stefan Hecht|2017|Chem.-Eur.J.|23|3743|doi:10.1002/chem.201605511
CCDC 1565864: Experimental Crystal Structure Determination
Related Article: Chung-Yang Huang, Aurelio Bonasera, Lachezar Hristov, Yves Garmshausen, Bernd M. Schmidt, Denis Jacquemin, Stefan Hecht|2017|J.Am.Chem.Soc.|139|15205|doi:10.1021/jacs.7b08726