Photometric Detection of Nitric Oxide Using a Dissolved Iron(III) Corrole as a Sensitizer

Fischer, Stefan; Vestfrid, Jenya; Mahammed, Atif; Herrmann‐Westendorf, Felix; Schulz, Martin; Müller, Jürgen; Kiesewetter, Olaf; Dietzek, Benjamin; Gross, Zeev; Presselt, Martin

doi:10.1002/cplu.201500553

Cited by 13 publications

(29 citation statements)

References 114 publications

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“…Supramolecular structures of dyes used for optical layers, − active layers in organic, − dye sensitized, − or hybrid solar cells − (OSCs, DSSCs, HSCs, respectively), sensors, , as well as organic light emitting diodes ,− (OLEDs) essentially determine the resulting thin film − and device properties . While the molecular interactions between many dyes with extended π-systems are governed by dispersion interactions, the interactions between push–pull dyes, such as merocyanines, , are typically dominated by dipole–dipole interactions .…”

Section: Introductionmentioning

confidence: 99%

Photoannealing of Merocyanine Aggregates

et al. 2018

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In this work we elucidate the fundamental difference between aggregate formation of donor−π–acceptor merocyanines in their electronic ground and excited states. While increasing the π-bridge size favors formation of π-stacked aggregates in the dark, irradiation with visible light causes reorientation of the dyes to form prototype H-aggregates with compensating dipole moments. This photoannealing changes the supramolecular structure and its UV–vis spectroscopic properties dramatically, thus being of importance for the function of active layers composed of these dyes. Aggregates of the ground state dyes are bound cooperatively through ππ-London dispersion interactions and hydrogen bonds between the polar α-cyano-carboxylic acid groups. However, charge transfer upon photoexcitation leads to repulsion of the polar acid groups. Electronic excitation of the dyes approximately doubles the ground state dipole moment, thus driving molecular reorientation into prototype H-aggregate structures. We show that this photoinduced supramolecular rearrangement can disrupt the large polymeric aggregates formed in the dark. The photoinduced supramolecular structural changes reported in this work will influence the performance of optoelectronic devices composed of these structures and must be controlled to avoid morphological decomposition of active layers upon operation.

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Section: Introductionmentioning

confidence: 99%

Photoannealing of Merocyanine Aggregates

et al. 2018

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“…The versatile photophysical properties [1][2][3] and chelating abilities of corroles render this class of molecules of high interest for numerous applications [4][5] , such as novel catalysts [6][7][8][9] , antitumor and imaging agents [10][11][12] , molecular sensors [13][14][15][16][17] and optoelectronic devices [18][19][20] . Corroles are macrocycles that, similar to porphyrins, contain four pyrrole rings 21 .…”

Section: Introductionmentioning

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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“…Supramolecular structures of dyes have a large impact on the optoelectronic properties of organic layers. − To achieve high degrees of supramolecular order, different methods have been established where amphiphilic dyes are first assembled at interfaces, such as liquid–liquid interface precipitation (LLIP) , and Langmuir − techniques, and subsequently deposited on surfaces, e.g., electrodes needed for optoelectronic devices ,− and sensors. − The Langmuir technique allows for precise control of packing densities and molecular orientations in quasi-two-dimensional layers formed at the air–water interface. Prototype optically active Langmuir layers are made from amphiphilic dyes.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Reorientation During Deposition Onto Metal Surfaces of Quasi-Two-Dimensional Langmuir Monolayers Composed of Bifunctional Amphiphilic, Twisted Perylenes

et al. 2021

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Supramolecular dye structures, which are often ruled by π−π interactions between planar chromophores, crucially determine the optoelectronic properties of layers and interfaces. Here, we present the interfacial assembly of perylene monoanhydride and monoimide that do not feature a planar chromophore but contain chlorine substituents in the bay positions to yield twisted chromophores and hence modified π-stacking. The assembly of the twisted perylene monoanhydride and monoimide is driven by their amphiphilicity that ensures proper Langmuir layer formation. The shielding of the hydrophilic segment upon attaching an alkyl chain to the imide moiety yielded a more rigid Langmuir layer, even though the degrees of freedom were increased due to this modification. For the characterization of the Langmuir layer's supramolecular structure, the layers were deposited onto glass, silver, and gold substrates via Langmuir−Blodgett (LB) and Langmuir−Schaefer (LS) techniques and were investigated with atomic force microscopy and surface-enhanced resonance Raman spectroscopy (SERRS). From the similarity between all SERR spectra of the LS and LB layers, we concluded that the perylenes have changed their orientation upon LB deposition to bind to the silver surface of the SERRS substrate via sulfur atoms. In the Langmuir layer, the perylenes, which are πstacked with half of the twisted chromophores, must already be inclined and cannot achieve full parallel alignment because of the twisting-induced steric hindrance. However, upon rotation, the energetically most favorable antiparallel aligned structures can be formed and bind to the SERRS substrate. Thus, we present, to the best of our knowledge, the first fabrication of quasi-twodimensional films from twisted amphiphilic perylene monoimides and their reassembly during LB deposition. The relation between the molecular structure, supramolecular interfacial assembly, and its adoption during adsorption revealed here is crucial for the fabrication of defined functionalizations of metal surfaces, which is key to the development of organic (opto)electronic devices.

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Photometric Detection of Nitric Oxide Using a Dissolved Iron(III) Corrole as a Sensitizer

Cited by 13 publications

References 114 publications

Photoannealing of Merocyanine Aggregates

Photoannealing of Merocyanine Aggregates

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

Supramolecular Reorientation During Deposition Onto Metal Surfaces of Quasi-Two-Dimensional Langmuir Monolayers Composed of Bifunctional Amphiphilic, Twisted Perylenes

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