Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C18 to C16
Chemistry. 2024 Mar 26:e202400215. doi: 10.1002/chem.202400215. Online ahead of print.ABSTRACTRecent advances in synthetic methods, combined with tip-induced on-surface chemistry, have enabled the formation of numerous cyclocarbon molecules. Here, we investigate computationally the experimentally studied C16 and C18 molecules as well as their van der Waals (vdW) complexes with several typical donor and acceptor molecules. Our results demonstrate a remarkable electron-withdrawing ability of cyclocarbon molecules. The vdW complexes of C16 and C18 exhibit a thermodynamically favorable photoinduced electron transfer (ET) from ...
Source: Chemistry - March 26, 2024 Category: Chemistry Authors: Olga A Stasyuk Alexander A Voityuk Anton J Stasyuk Source Type: research

Enhancing Intramolecular Ferromagnetic Coupling in Tetrathiafulvalene-Nitronyl Nitroxide-based Compounds through Spin Polarization Mechanism
Chemistry. 2024 Mar 26:e202400166. doi: 10.1002/chem.202400166. Online ahead of print.ABSTRACTSpin-polarized-donor radicals based on tetrathiafulvalene (TTF) and nitronyl-nitroxide (NN) in which one-electron oxidation involves the HOMO instead of the SOMO are well-known for exhibiting magnetoresistance. In particular, BTBN consists of one dibromo-TTF and one NN radical, which are linked by a phenyl coupler group. One of the key factors driving magnetoresistance is the presence of intramolecular ferromagnetic (FM) coupling between the TTF+•-oxidized π-donor (D-unit) and NN (R-unit). Here, a theoretical study is conducted...
Source: Chemistry - March 26, 2024 Category: Chemistry Authors: Pau Franquesa-Vi ñas Jordi Ribas-Ari ño Raul Santiago Merc è Deumal Source Type: research

A General Concept for the Electronic and Steric Modification of 1-Metallacyclobuta-2,3-dienes: A Case Study of Group 4 Metallocene Complexes
We present the synthesis of two Ph substituted dilithiated ligand precursors for the preparation of four new 1-metallacyclobuta-2,3-dienes [rac-(ebthi)M] (M=Ti, Zr; ebthi=1,2-ethylene-1,10-bis(η5-tetrahydroindenyl)). The organolithium compounds [Li2(RC3Ph)] (1b: R = Ph, 1c: R = SiMe3) as well as the metallacycles of the general formula [rac-(ebthi)M(R1C3R2)] (2b: M=Ti, R1=R2=Ph, 2c: M=Ti, R1=Ph, R2=SiMe3; 3b: M=Zr, R1=R2=Ph; 3c: M=Zr, R1=Ph, R2=SiMe3) were fully characterised. Single crystal X-ray diffraction and quantum chemical bond analysis of the Ti and Zr complexes reveal ligand influence on the biradicaloid characte...
Source: Chemistry - March 26, 2024 Category: Chemistry Authors: Sihan Li Mirjam Schr öder Adrian Prudlik Xinzhe Shi Anke Spannenberg Jabor Rabeah Robert Francke Bj örn Corzilius Fabian Rei ß Torsten Beweries Source Type: research

One-pot Synthesis of PdCuAg and CeO2 Nanowires Hybrid with Abundant Heterojunction Interface for Ethylene Glycol Electrooxidation
Chemistry. 2024 Mar 26:e202400944. doi: 10.1002/chem.202400944. Online ahead of print.ABSTRACTIntroducing CeO2 into Pd-based nanocatalysts for electrocatalytic reactions is a good way to solve the intermediate toxicity problem and improve the catalytic performance. Here we reported a simple strategy to synthesize the PdCuAg and CeO2 nanowires hybrid via one-pot synthesis process under strong nanoconfined effect of specific surfactant as templates. Owing to the structural (ultrathin nanowires, abundant heterojunction/interfaces between metal and metal oxide) and compositional (Pd, Cu, Ag, CeO2) advantages, the hybrid showed...
Source: Chemistry - March 26, 2024 Category: Chemistry Authors: Dongping Fan Jinyu Zheng Xin Xiang Dongdong Xu Source Type: research

Surface-Enhanced Raman Scattering Using 2D Materials
Chemistry. 2024 Mar 26:e202303658. doi: 10.1002/chem.202303658. Online ahead of print.ABSTRACTThe use of surface-enhanced Raman scattering (SERS) as a technique for detecting small amounts of (bio)chemical analytes has become increasingly popular in various fields. While gold and silver nanostructures have been extensively studied as SERS substrates, the availability of other types of substrates is currently expanding the applications of this spectroscopic method. Recently, researchers have begun exploring two-dimensional (2D) materials (e.g., graphene-like nanostructures) as substrates for SERS analysis. These materials o...
Source: Chemistry - March 26, 2024 Category: Chemistry Authors: Beatriz Pinto de Sousa Sara Isabel Augusto Fateixa Tito Trindade Source Type: research

Mono-ortho-beryllated Carbodiphosphoranes:  Synthesis, Structure, Bonding and Reactivity
Chemistry. 2024 Mar 26:e202400966. doi: 10.1002/chem.202400966. Online ahead of print.ABSTRACTThe reaction of organoberyllium compounds with hexaphenylcarbodiphosphorane yields mono-ortho-beryllated complexes, which feature a double dative Be=C bond. The bonding situation in these compounds together with a simple carbodiphosphorane and an N-heterocyclic carbene adduct was analysed with energy decomposition analysis in combination with natural orbital for chemical valence as well as with quantum theory of atoms-in-molecules. Furthermore, the driving forces accountable for mono-ortho-beryllation were elucidated along with th...
Source: Chemistry - March 26, 2024 Category: Chemistry Authors: Magnus Richard Buchner Lukas K Kreuzer Lewis R Thomas-Hargreaves Matthias M üller Sergei I Ivlev Gernot Frenking Sudip Pan Source Type: research

Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C18 to C16
Chemistry. 2024 Mar 26:e202400215. doi: 10.1002/chem.202400215. Online ahead of print.ABSTRACTRecent advances in synthetic methods, combined with tip-induced on-surface chemistry, have enabled the formation of numerous cyclocarbon molecules. Here, we investigate computationally the experimentally studied C16 and C18 molecules as well as their van der Waals (vdW) complexes with several typical donor and acceptor molecules. Our results demonstrate a remarkable electron-withdrawing ability of cyclocarbon molecules. The vdW complexes of C16 and C18 exhibit a thermodynamically favorable photoinduced electron transfer (ET) from ...
Source: Chemistry - March 26, 2024 Category: Chemistry Authors: Olga A Stasyuk Alexander A Voityuk Anton J Stasyuk Source Type: research

Enhancing Intramolecular Ferromagnetic Coupling in Tetrathiafulvalene-Nitronyl Nitroxide-based Compounds through Spin Polarization Mechanism
Chemistry. 2024 Mar 26:e202400166. doi: 10.1002/chem.202400166. Online ahead of print.ABSTRACTSpin-polarized-donor radicals based on tetrathiafulvalene (TTF) and nitronyl-nitroxide (NN) in which one-electron oxidation involves the HOMO instead of the SOMO are well-known for exhibiting magnetoresistance. In particular, BTBN consists of one dibromo-TTF and one NN radical, which are linked by a phenyl coupler group. One of the key factors driving magnetoresistance is the presence of intramolecular ferromagnetic (FM) coupling between the TTF+•-oxidized π-donor (D-unit) and NN (R-unit). Here, a theoretical study is conducted...
Source: Chemistry - March 26, 2024 Category: Chemistry Authors: Pau Franquesa-Vi ñas Jordi Ribas-Ari ño Raul Santiago Merc è Deumal Source Type: research

Ferromagnetically coupled chromium(III) dimer shows luminescence and sensitizes photon upconversion
Chemistry. 2024 Mar 25:e202400856. doi: 10.1002/chem.202400856. Online ahead of print.ABSTRACTThere has been much progress on mononuclear chromium(III) complexes featuring luminescence and photoredox activity, but dinuclear chromium(III) complexes have remained underexplored in these contexts until now. We identified a tridentate chelate ligand able to accommodate both meridional and facial coordination of chromium(III), to either access a mono- or a dinuclear chromium(III) complex depending on reaction conditions. This chelate ligand causes tetragonally distorted primary coordination spheres around chromium(III) in both c...
Source: Chemistry - March 25, 2024 Category: Chemistry Authors: Simon Trippmacher Serhiy Demeshko Alessandro Prescimone Franc Meyer Oliver S Wenger Cui Wang Source Type: research

Chiral Spiro-Tetrathiafulvalenes: Synthesis, Chiroptical Properties, Conformational Issues and Charge Transfer Complexes
Chemistry. 2024 Mar 25:e202400564. doi: 10.1002/chem.202400564. Online ahead of print.ABSTRACTWithin this work we have investigated spiro-based tetrathiafulvalenes (TTFs) obtained as mixtures of stereoisomers from racemic spiro[5.5]undeca-1,8-dien-3-one. Compared to previously described spiro-TTFs, enantiomeric and diastereoisomeric forms have been here separated by chiral HPLC and fully characterized both experimentally and theoretically. The two types of spiro-based chiral derivatives contain either one (2) or three (1) chiral centres out of each one is spiro-type. Experimental CD, supported by TD-DFT calculations, shows...
Source: Chemistry - March 25, 2024 Category: Chemistry Authors: Alexandra Bogdan Ionut-Tudor Moraru Nicolas Vanthuyne Pascale Auban-Senzier Ion Grosu Narcis Avarvari Flavia Pop Source Type: research

Increasing dimensionality in self-assembly. Toward two-dimensional supramolecular polymers
Chemistry. 2024 Mar 25:e202400379. doi: 10.1002/chem.202400379. Online ahead of print.ABSTRACTDifferent approaches to achieve 2D supramolecular polymers, as an alternative to the covalent bottom-up approaches reported for the preparation of 2D materials, are reviewed. The significance of the operation of weak non-covalent forces to induce a lateral growth of a number of self-assembling units is collected. The examples of both thermodynamically and kinetically controlled formation of 2D supramolecular polymers showed in this review demonstrate the utility of this strategy to achieve new 2D materials with biased morphologies...
Source: Chemistry - March 25, 2024 Category: Chemistry Authors: Carmen Mar ía Atienza Luis Sanchez Source Type: research

A Photoswitchable Metallocycle Based on Azobenzene: Synthesis, Characterization, and Ultrafast Dynamics
Chemistry. 2024 Mar 25:e202400205. doi: 10.1002/chem.202400205. Online ahead of print.ABSTRACTThe novel photoswitchable ligand 3,3'-Azobenz(metPA)2 (1) is used to prepare a [Cu2(1)2](BF4)2 metallocycle (2), whose photoisomerization was characterized using static and time-resolved spectroscopic methods. Optical studies demonstrate the highly quantitative and reproducible photoinduced cyclic E/Z switching without decay of the complex. Accordingly and best to our knowledge, [Cu2(1)2](BF4)2 constitutes the first reversibly photoswitchable (3d)‑metallocycle based on azobenzene. The photoinduced multiexponential dynamics in th...
Source: Chemistry - March 25, 2024 Category: Chemistry Authors: Raphael I Petrikat Justin Hornbogen Marcel J P Schmitt Emma Resmann Christina Wiedemann Nesrin I Dilmen Heinrich Schneider Annika M Pick Christoph Riehn Rolf Diller Sabine Becker Source Type: research

Secondary sites of the C-type lectin-like fold
Chemistry. 2024 Mar 25:e202400660. doi: 10.1002/chem.202400660. Online ahead of print.ABSTRACTC-type lectins are a large superfamily of proteins involved in a multitude of biological processes. In particular, their involvement in immunity and homeostasis has rendered them attractive targets for diverse therapeutic interventions. They share a characteristic C-type lectin-like domain whose adaptability enables them to bind a broad spectrum of ligands beyond the originally defined canonical Ca2+-dependent carbohydrate binding. Together with variable domain architecture and high-level conformational plasticity, this enables C-...
Source: Chemistry - March 25, 2024 Category: Chemistry Authors: Jonathan Lefebre Torben Falk Yunzhan Ning Christoph Rademacher Source Type: research

Electrochemical Dehydration of Dicarboxylic Acids to Their Cyclic Anhydrides
Chemistry. 2024 Mar 25:e202400403. doi: 10.1002/chem.202400403. Online ahead of print.ABSTRACTAn intramolecular electrochemical dehydration reaction of dicarboxylic acids to their cyclic anhydrides is presented. This electrolysis allows dicarboxylic acids as naturally abundant, inexpensive, safe, and readily available starting materials to be transformed into carboxylic anhydrides under mild reaction conditions. No conventional dehydration reagent is required. The obtained cyclic anhydrides are highly valuable reagents in organic synthesis, and in this report, we use them in-situ for acylation reactions of amines to synthe...
Source: Chemistry - March 25, 2024 Category: Chemistry Authors: Johannes Schneider Andreas P H äring Siegfried R Waldvogel Source Type: research

Accelerating Cellular Uptake with Unnatural Amino Acid for Inhibiting Immunosuppressive Cancer Cells
Chemistry. 2024 Mar 25:e202400691. doi: 10.1002/chem.202400691. Online ahead of print.ABSTRACTTargeting immunosuppressive metastatic cancer cells is a key challenge in therapy. We recently have shown that a rigid-rod aromatic, pBP-NBD, that responds to enzymes and kill immunosuppressive metastatic osteosarcoma (mOS) and castration resistant prostate cancer (CRPC) cells in mimetic bone microenvironment. However, pBP-NBD demonstrated moderate efficacy against CRPC cells. To enhance activity, we incorporated the unnatural amino acid L- or D-4,4'-biphenylalanine (L- or D-BiP) into pBP-NBD, drastically increasing cellular uptak...
Source: Chemistry - March 25, 2024 Category: Chemistry Authors: Meihui Yi Gabriel Ashton-Rickardt Weiyi Tan Zhiyu Liu Hongjian He Jer-Tsong Hsieh Bing Xu Source Type: research