Search

Molecular platforms are essential components of various surface‐mounted molecular devices. Here, we document the synthesis of two universal triptycene‐based tripodal pedestals featuring terminal alkynes in the axial position. We showcase their versatility by incorporating them into the structures of diverse functional molecules such as unidirectional light‐driven molecular motors, photoswitches, and Brownian molecular rotors using standard cross‐coupling reactions. We also present their fundamental physical properties, including acidity constants, data from differential scanning calorimetry, and crystallographic analysis of two parent and five derived structures. Finally, and importantly, we demonstrate that the photochemical properties of selected photoswitch representatives remain uncompromised when fused with tripods. [ABSTRACT FROM AUTHOR]

Cholesterol plays an important biological role in the body, and its disruption in homeostasis and synthesis has been implicated in several diseases. Mapping the locations of cholesterol is crucial for gaining a better understanding of these conditions. Silver deposition has proven to be an effective method for analyzing cholesterol using mass spectrometry imaging (MSI). We optimized and evaluated thermal evaporation as an alternative deposition technique to sputtering for silver deposition in MSI of cholesterol. A silver layer with a thickness of 6 nm provided an optimal combination of cholesterol signal intensity and mass resolution. The deposition of an ultrathin nanofilm of silver enabled high-resolution MSI with a pixel size of 10 µm. We used this optimized method to visualize the distribution of cholesterol in the senile plaques in the brains of APP/PS1 mice, a model that resembles Alzheimer's disease pathology. We found that cholesterol was evenly distributed across the frontal cortex tissue, with no evidence of plaque-like accumulation. Additionally, we investigated the presence and distribution of cholesterol in myocardial sections of a human heart affected by wild-type ATTR amyloidosis. We identified the presence of cholesterol in areas with amyloid deposition, but complete colocalization was not observed. [ABSTRACT FROM AUTHOR]

2,9‐ and 2,10‐diphenylpentacene were synthesized by direct C−H borylation of ketal‐protected pentacene, followed by halodeboronation, resolution of the dihalo isomers, Suzuki arylation, cleavage of the ketals and decarbonylation in the solid state. They were studied as main active components in organic field effect transistors (OFETs). Diphenyl substitution of pentacene affects the unit cell dimensions only slightly, preserving a face to edge molecular packing in the first layers of thin films evaporated on SiO2 substrates. Both isomers self‐assemble into nanoribbons during the thin film growth upon vapor deposition. The similarity between the surface induced phases of the 2,9‐isomer and unsubstituted pentacene leads to similar 4‐probe hole mobilities, i. e. 0.13 cm2 V−1 s−1 for the former. Whereas 2,9‐disubstitution thus does essentially preserve the thin film characteristics of unsubstituted pentacene, 2,10‐disubstitution is detrimental to the molecular ordering in the thin films and therefore to the field effect mobility which is only 0.07 cm2 V−1 s−1. The known strong enhancement of field effect mobility observed upon diphenyl substitution of anthracene can thus not be emulated analogously with pentacene. [ABSTRACT FROM AUTHOR]

This article discusses the synthesis of triptycene-based tripodal molecular platforms, which are important for surface-mounted molecular devices. These molecular tripods have been shown to be versatile by being integrated into various functional molecules, such as molecular motors, photoswitches, and molecular rotors. The researchers achieved this by using standard cross-coupling reactions. For more information, readers can refer to the research article by J. Kaleta and co-workers. [Extracted from the article]

Taurine (2-aminoethanesulfonic acid) is a representative substructure in biologically active compounds, but can raise difficulties in direct coupling reactions. In this study, the synthesis of taurine-derived sulfonic acids and analogous aromatic sulfonic acids was accomplished by a performic acid promoted oxidation of corresponding symmetrical disulfide precursors. In some of the products, the taurine or sulfanilic acid nitrogen atom is incorporated in a heterocyclic scaffold or part of a peptide bond in dipeptide mimetics. [ABSTRACT FROM AUTHOR]

Molecular platforms are essential components of various surface-mounted molecular devices. Here, we document the synthesis of two universal triptycene-based tripodal pedestals featuring terminal alkynes in the axial position. We showcase their versatility by incorporating them into the structures of diverse functional molecules such as unidirectional light-driven molecular motors, photoswitches, and Brownian molecular rotors using standard cross-coupling reactions. We also present their fundamental physical properties, including acidity constants, data from differential scanning calorimetry, and crystallographic analysis of two parent and five derived structures. Finally, and importantly, we demonstrate that the photochemical properties of selected photoswitch representatives remain uncompromised when fused with tripods., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Despite recent tremendous progress in the synthesis of nonplanar chiral aromatics, and helicenes in particular, their conversion to half-sandwich or sandwich transition metal complexes still lags behind, although they represent an attractive family of modular and underexplored chiral architectures with a potential catalytic use. In this work, starting from various chiral helicene-indene proligands, we prepared the enantio- and diastereopure oxa[6]- and oxa[7]helicene-indenido half-sandwich RhI and RhIII complexes and oxa[7]helicene-bisindenido ansa-metallocene FeII complex. To document their use, oxahelicene-indenido half-sandwich RhIII complexes were employed as chiral catalysts in enantioselective C-H arylation of benzo[h]quinolines with 1-diazonaphthoquinones to afford a series of axially chiral biaryls in mostly good to high yields and in up to 96 : 4 er. Thus, we developed stereocontrolled synthesis of chiral helicene-indenido ansa- and half-sandwich metal complexes, successfully demonstrated the first use of such helicene Cp-related metal complexes in enantioselective catalysis, and described an unusual sequence of efficient central-to-helical-to-planar-to-axial chirality transfer., (© 2024 Wiley‐VCH GmbH.)

Racemic and highly enantioenriched 3-methoxycarbonyl, 3-carboxy, and 3-hydroxymethyl derivatives of dibenzo[6]helicene were prepared. The Langmuir layers of these helicenes were formed at the air-water interface and transferred onto solid substrates to afford Langmuir-Blodgett films, which were then studied by ambient atomic force microscopy and (chir)optical spectroscopy. Significant differences were found in the behaviour of the Langmuir layers as well as in the morphology, UV/Vis, electronic circular dichroism (ECD), and fluorescence spectra of the Langmuir-Blodgett thin films depending on the molecular chirality and nature of the polar group. The experimental results were supported by molecular dynamics simulations., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Helical chirality is a novel enantioselectivity-inducing property in transition-metal-catalyzed transformations. The principle is illustrated herein for the example of asymmetric olefin metathesis. This work reports the synthesis of the first helically chiral Ru-NHC alkylidene complex from an aminohelicene-derived imidazolium salt, which was ligated to the first generation Hoveyda-Grubbs catalyst. Kinetic data were acquired for benchmark test reactions and compared to an achiral catalyst. The helically chiral Ru-catalyst was evaluated in asymmetric ring-closing metathesis (RCM) and ring-opening metathesis-cross-metathesis (ROM/CM) reactions, which proceeded with promising levels of enantioselectivity. Extensive NMR-spectroscopic investigations and a DFT geometry optimization were performed. These results led to a topographic steric map and calculation of percent-buried-volume values for each quadrant around the metal center., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of oxahelicenes composed of ortho/meta-annulated benzene/pyridine and 2H-pyran rings were synthesized on the basis of the cobalt(I)-mediated (or rhodium(I)- or nickel(0)-mediated) double, triple, or quadruple [2+2+2] cycloisomerization of branched aromatic hexa-, nona-, or dodecaynes, thus allowing the construction of 6, 9, or 12 rings in a single operation. The use of a flow reactor was found to be beneficial for the multicyclization reactions. The stereogenic centers present in some of the oligoynes steered the helical folding in such a way that the final oxa[9]-, [13]-, [17]- and [19]helicenes were obtained in both enantiomerically and diastereomerically pure form. Specifically, the oxa[19]helicenes beat the current record in the length of a helicene backbone. Single-molecule conductivity was studied by the mechanically controllable break-junction method with a pyridooxa[9]helicene., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Chimerical pyrene-based dibenzo[7]helicene rac-1 and 2H-pyran[7]helicene (M,R,R)-(-)-2, in which two pyrene subunits are fused to the [7]helicene/[7]heterohelicene scaffold, were synthesised by means of Ni(0) - or Co(I) -mediated [2+2+2] cycloisomerisation of dipyrenyl-acetylene-derived triynes. Pyrene-based dibenzo[7]helicene 1 was obtained in enantioenriched form by enantioselective cycloisomerisation under Ni(0) /QUINAP catalysis (57 % ee) or in enantiopure form by racemate resolution by liquid chromatography on a chiral column. 1,3-Allylic-type strain-controlled diastereoselective cycloisomerisation was employed in the synthesis of enantiopure (M,R,R)-(-)-2. Physicochemical properties of 1 and 2 encompassing the helicity assignment, stability to racemisation, X-ray crystal structure, UV/Vis, experimental/calculated electronic circular dichroism and fluorescence spectra were studied. Accordingly, comparison of the X-ray crystal structure of (M,R,R)-(-)-2 with calculated structures (DFT: B3LYP/cc-pVDZ, B97D/cc-pVDZ) indicated that its helical backbone is slightly over-flattened owing to intramolecular dispersion forces between tert-butylated pyrene subunits. Both 1 and 2 are fluorescent (with quantum yields in dichloromethane of ΦF =0.10 and 0.17, respectively) and are suggested to form intramolecular excimer states upon excitation, which are remarkably stabilised and exhibit large Stokes shifts (296 and 203 nm, respectively)., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)