Tuning the polarity and surface activity of hydroxythiazoles – extending the applicability of highly fluorescent self-assembling chromophores to supra-molecular photonic structures

Habenicht, Stefanie H.; Schramm, Stefan; Fischer, Stefan; Sachse, Torsten; Herrmann‐Westendorf, Felix; Bellmann, Andrea; Dietzek, Benjamin; Presselt, Martin; Weiss, Dieter G.; Beckert, Rainer; Görls, Helmar

doi:10.1039/c5tc03632a

Cited by 31 publications

(36 citation statements)

References 79 publications

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“…The amphiphilic character is visualized by the quantum mechanically calculated electrostatic potential distribution ϕ(r) derived from the electron density distribution [58][59][60] at the van der Waals (vdW) surface (for computational details, see methods section) in Figure 1. From electrostatic potential and charge distributions on vdW surfaces, solubilities as well as reactivities can be estimated [61][62][63] , cf. the seminal work of Klamt et al on the analysis of screening counter charges in conductor environments.…”

Section: Polarity Of the Different Corrole Speciesmentioning

confidence: 99%

Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations

et al. 2017

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Corroles are emerging as an important class of macrocycles with numerous applications because of their peculiar photophysical and metal chelating properties. meso-Pyrimidinylcorroles are easily deprotonated in certain solvents, which changes their absorption and emission spectra as well as their accessible supramolecular structures. To enable control over the formation of supramolecular structures, the dominant corrole species, i.e., the deprotonated form or one of the two NH-tautomers, needs to be identified. Therefore, we focus in the present article on the determination of the UV-vis spectroscopic properties of the free-base NH-tautomers and the deprotonated form of a new amphiphilic meso-pyrimidinylcorrole that can assemble to supramolecular structures at heterointerfaces as utilized in the Langmuir-Blodgett and liquid-liquid interface precipitation techniques. After quantification of the polarities of the free-base NH-tautomers and the deprotonated form by means of quantum chemically derived electrostatic potential distributions at the corroles' van der Waals surfaces, the preferential stabilization of (some of) the considered species in solvents of different polarity is identified by means of absorption spectroscopy. For the solutions with complex mixtures of species, we applied fluorescence excitation spectroscopy to estimate the relative weights of the individual corrole species. This technique might also be applied to identify dominating species in molecularly thin films directly on the subphase' surface of Langmuir-Blodgett troughs. Supported by quantum chemical calculations we were able to differentiate between the spectral signatures of the individual NH-tautomers by means of fluorescence excitation spectroscopy.

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Section: Polarity Of the Different Corrole Speciesmentioning

confidence: 99%

Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations

et al. 2017

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“…Solubility in polar solvents such as water can be obtained through simple sulfonation or chlorosulfonation and subsequent transformation into respective sulfonamides. 13 The hydroxyl functionality, here present as ethyl, butyl-, or hexyl ethers, can also be used to install numerous reactive groups (e.g., azides, isothiocyanates, NHS esters etc. ), as shown for a molecular probe with an azide substructure for the mass-and fluorescence spectrometric detection of certain natural products.…”

Section: Paper Syn Thesis Table 1 Absorption and Emission Properties mentioning

confidence: 99%

Small Molecules as Long-Wavelength Fluorophores: Push-Pull Substituted 4-Alkoxy-1,3-thiazoles

et al. 2017

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A series of donor-pi-acceptor (D-pi-A) substituted 4-hydroxythiazoles have been synthesized. Electron-donating groups (4-methoxyphenyl and 4-dimethylaminophenyl) were installed in the 5-position of the thiazole; thiophene/pyridine-bridged acceptors (formyl groups and their Knoevenagel condensation products) were placed in the 2-position. The influence of D-pi-A character on the photophysical properties and electronic structure was investigated by means of UV/Vis and fluorescence spectroscopy

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“…In this work, we focus on terphenylene carboxylic acid ( TPCA ) as a π-conjugated matrix amphiphile and stearic acid ( SA ) for reference. As an amphiphilic dye, we choose a 4-hydroxy thiazole − (see Figure ), whose 4-hydroxy position is connected to a hydrophilic carboxylic acid moiety via a flexible decyl chain that adds motional degrees of freedom during supramolecular structure formation in Langmuir layers. ,, This 4-hydroxy thiazole derivative, labeled 10 because of the number of CH 2 groups constituting the linker, hence consists of a chromophore bearing three aromatic rings and an alkylic acid. Following the “like dissolves like” rule, which can be explained via analysis of electrostatic surface potentials − and finally the “conductor-like screening model for real solutions”, − fatty acids or linear aromatic amphiphiles are chemically similar to the alkyl chain and the chromophore of 10 , respectively.…”

Section: Introductionmentioning

confidence: 99%

Embedding an Amphiphilic 4-Hydroxy Thiazole Dye in Langmuir Matrices: Studying Miscibilities with Arylic and Alkylic Matrix Amphiphiles via Langmuir Isotherms and Photo-induced Force Microscopy

et al. 2021

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We present here a fundamental study on the miscibility between a prototype amphiphilic dye and alkylic and arylic Langmuir monolayers. Embedding dyes in such matrices is crucial for utilizing dyes in any photo-energy conversion process if the involved dyes form aggregates that provide thermal deactivation channels. Because miscibility in Langmuir matrices depends on the blending ratio between the dye and matrix and on the Langmuir film density, as characterized via the surface pressure and the mean molecular area, we employ Langmuir miscibility studies to identify ideal miscibility parameters for each matrix. Atomic force microscopy (AFM) results support miscibility between the dye and both matrix materials at low surface pressures, where smooth and homogeneous films are obtained. AFM and photo-induced force microscopy (PiFM) reveal phase separation if the Langmuir monolayers are deposited at surface pressures above 8 mN/m at which reorientation of the chromophores has been reported. The nanoscale chemical fingerprint mapping enabled by PiFM enables assigning segregated spots to small stearic acid (SA)-enriched domains that have not been detected via AFM, thus demonstrating the value of the IR-spectroscopic contrast provided by PiFM. In this work, we have presented a so far unexploited matrix material (terphenylene carboxylic acid; TPCA) and found it equally suitable for embedding dyes as the standard amphiphile SA. In contrast to SA, TPCA is composed of rigid and electrically conducting π-electron systems, hence, being predestined for aligning dyes in Langmuir matrices and for application in optoelectronic systems.

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Tuning the polarity and surface activity of hydroxythiazoles – extending the applicability of highly fluorescent self-assembling chromophores to supra-molecular photonic structures

Abstract: Processing of 4-alkoxythiazole sulfonamidesviathe Langmuir–Blodgett technique gave an insight into the influence of aggregation on the electro-optical properties of thin films.

Cited by 31 publications

References 79 publications

Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations

Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations

Small Molecules as Long-Wavelength Fluorophores: Push-Pull Substituted 4-Alkoxy-1,3-thiazoles

Embedding an Amphiphilic 4-Hydroxy Thiazole Dye in Langmuir Matrices: Studying Miscibilities with Arylic and Alkylic Matrix Amphiphiles via Langmuir Isotherms and Photo-induced Force Microscopy

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