Search results for "540 Chemie und zugeordnete Wissenschaften"
showing 9 items of 9 documents
Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes.
2018
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…
PyDSC: a simple tool to treat differential scanning calorimetry data
2020
AbstractHerein, we describe an open-source, Python-based, script to treat the output of differential scanning calorimetry (DSC) experiments, called pyDSC, available free of charge for download at https://github.com/leonardo-chiappisi/pyDSC under a GNU General Public License v3.0. The main aim of this program is to provide the community with a simple program to analyze raw DSC data. Key features include the correction from spurious signals, and, most importantly, the baseline is computed with a robust, physically consistent approach. We also show that the baseline correction routine implemented in the script is significantly more reproducible than different standard ones proposed by propriet…
Light-controlled reversible modulation of frontier molecular orbital energy levels in trifluoromethylated diarylethenes
2017
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…
Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes
2020
Crown ethers are common building blocks in supramolecular chemistry and are frequently applied as cation sensors or as subunits in synthetic molecular machines. Developing switchable and specifically designed crown ethers enables the implementation of function into molecular assemblies. Seven tailor-made redox-active crown ethers incorporating tetrathiafulvalene (TTF) or naphthalene diimide (NDI) as redox-switchable building blocks are described with regard to their potential to form redox-switchable rotaxanes. A combination of isothermal titration calorimetry and voltammetric techniques reveals correlations between the binding energies and redox-switching properties of the corresponding ps…
Protonenvermittelter Ringschluss eines negativ photochromen, Azulen‐basierten Diarylethens
2020
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…
Near-IR to Near-IR Upconversion Luminescence in Molecular Chromium Ytterbium Salts
2020
Abstract Upconversion photoluminescence in hetero‐oligonuclear metal complex architectures featuring organic ligands is an interesting but still rarely observed phenomenon, despite its great potential from a basic research and application perspective. In this context, a new photonic material consisting of molecular chromium(III) and ytterbium(III) complex ions was developed that exhibits excitation‐power density‐dependent cooperative sensitization of the chromium‐centered 2E/2T1 phosphorescence at approximately 775 nm after excitation of the ytterbium band 2F7/2→2F5/2 at approximately 980 nm in the solid state at ambient temperature. The upconversion process is insensitive to atmospheric ox…
Light-Activated Sensitive Probes for Amine Detection
2017
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…
Proton‐Gated Ring‐Closure of a Negative Photochromic Azulene‐Based Diarylethene
2020
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. …
Surprising solvent-induced structural rearrangements in large [N⋯I+⋯N] halogen-bonded supramolecular capsules
2018
Coordinative halogen bonds have recently gained interest for the assembly of supramolecular capsules. Ion mobility-mass spectrometry and theoretical calculations now reveal the well-defined gas-phase structures of dimeric and hexameric [N...I+...N] halogen-bonded capsules with counterions located inside their cavities as guests. The solution reactivity of the large hexameric capsule shows the intriguing solvent-dependent equilibrium between the hexamer and an unprecedented pentameric [N...I+...N] halogen-bonded capsule, when the solvent is changed from chloroform to dichloromethane. The intrinsic flexibility of the cavitands enables this novel structure to adopt a pseudo-trigonal bipyramida…