Article
Chemistry, Physical
Seongwook Park, Seunghwan Byun, Huijeoung Ryu, Hyungwoo Hahm, Junseong Lee, Sukwon Hong
Summary: Novel ruthenium catalysts bearing azobenzene groups were developed for olefin metathesis reactions, demonstrating an on-off switching ability in ring-closing metathesis reactions depending on UV irradiation. Various types of olefin metathesis reactions, such as ring-opening metathesis, cross-metathesis, and ethenolysis, exhibited photoswitching phenomena. The reversible feature of photoswitching was confirmed by observing the photoisomerization of azobenzene-bearing cyclic(alkyl)(amino)carbene ligands and the corresponding ruthenium catalysts using UV-vis spectroscopy.
Article
Chemistry, Physical
Felix Ziegler, Hamzeh Kraus, Mathis J. Benedikter, Dongren Wang, Johanna R. Bruckner, Michal Nowakowski, Kilian Weisser, Helena Solodenko, Guido Schmitz, Matthias Bauer, Niels Hansen, Michael R. Buchmeiser
Summary: By utilizing cationic molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes confined in tailored ordered mesoporous silica, high macrocyclization selectivities up to 98% and high substrate concentrations up to 0.1 M can be achieved. Molecular dynamics simulations reveal that high conversions are a result of the proximity between the surface-bound catalyst and surface-located substrates, leading to increased reaction efficiency.
Review
Chemistry, Applied
Kamal M. Dawood, Kotohiro Nomura
Summary: This review article summarizes the effects of different catalysts on Z-selective olefin metathesis reactions and the essential roles of ligand modifications in achieving stereospecific reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Anna Kajetanowicz, Karol Grela
Summary: This paper introduces a novel subclass of chelating-benzylidene ruthenium catalysts that can be activated by electron-withdrawing groups, providing a highly tunable platform for target-oriented synthesis, medicinal chemistry, fine-chemicals preparation, and materials chemistry. The paper also offers suggestions for end-users on minimizing catalyst loading, controlling selectivity, and optimizing the olefin metathesis reaction based on examples provided.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Juan Pablo Martinez, Miquel Sola, Albert Poater
Summary: The research utilizes nanotechnology in olefin metathesis with homogeneous Ru-NHC catalysts, aiming to change the catalysis of the metal center to increase the steric pressure of C-60 in the first sphere of reactivity. DFT calculations show that SIMes-derived systems are efficient catalysts for olefin metathesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Janis Musso, Jordan De Jesus Silva, Mathis J. Benedikter, Jonas Groos, Wolfgang Frey, Christophe Coperet, Michael R. Buchmeiser
Summary: Recent studies have shown that cationic d(0) group 6 olefin metathesis catalysts exhibit higher activity compared to their neutral counterparts, and their catalytic performance is greatly enhanced by immobilization on silica.
Article
Chemistry, Multidisciplinary
Henrik Gulyas, Shigetaka Hayano, Adam Madarasz, Imre Papai, Mark Szabo, Agota Bucsai, Eddy Martin, Jordi Benet-Buchholz
Summary: By tuning the electron donor capacity of ligands, air-stable solid adducts of tungsten and molybdenum alkylidenes can be prepared, which can spontaneously release active catalysts in solution.
COMMUNICATIONS CHEMISTRY
(2021)
Article
Chemistry, Physical
Christian O. Blanco, Deryn E. Fogg
Summary: Water has a significant impact on olefin metathesis, as it can react with catalysts and cause decomposition of the reaction intermediates. This poses a challenge for demanding reactions in water-rich environments, as metathesis is typically noncatalytic under these conditions.
Article
Chemistry, Inorganic & Nuclear
Pavel A. Kumandin, Alexandra S. Antonova, Roman A. Novikov, Kirill A. Vasilyev, Marina A. Vinokurova, Mikhail S. Grigoriev, Anton P. Novikov, Daria K. Polianskaia, Kirill B. Polyanskii, Fedor I. Zubkov
Summary: This study investigates the synthesis and catalytic activity of ruthenium chelates with various heteroatoms in a six-membered ring. The researchers successfully prepared second-generation Hoveyda-Grubbs-type catalysts with a sulfur-ruthenium coordinate bond using standard procedures. They found that the trans-isomers of these catalysts showed excellent catalytic activity, outperforming the commercially available HG-II catalyst.
Article
Chemistry, Multidisciplinary
Stella A. Gonsales, Zoe C. Mueller, Fengyue Zhao, Paulo H. S. Paioti, Lydia Karmazin, Jing Wan, Fang Liu, K. N. Houk, Amir H. Hoveyda
Summary: The study reveals that phosphine-free Ru-CAAC complexes have the steric and electronic attributes to be highly effective in generating allenes, paving the way for the development of additional olefin metathesis reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Peng Ma, Jiaren Zhang, Xiaqian Wu, Jianhui Wang
Summary: Phosphine-free ruthenium benzylidene complexes with imidazole ligands have been reported. These catalysts are effective for high-temperature ring-closing metathesis (RCM) and cross-metathesis (CM) reactions, unlike the commonly used phosphine-containing N-heterocyclic carbene-based ruthenium catalysts which exhibit side reactions. This discovery paves the way for the development of more selective ruthenium metathesis catalysts for reactions requiring harsh conditions.
Article
Chemistry, Inorganic & Nuclear
Ignacio Sancho, Marta Navarro, Marc Montilla, Pedro Salvador, Cristina Santamaria, Josep M. Luis, Alberto Hernan-Gomez
Summary: In this study, a detailed route for the formation of titanium(III) orthophenylendiamido (PDA) species using [LiBHEt3] as a reducing agent is provided. These low-valent compounds in combination with [PPN]Cl are highly selective catalysts for the copolymerization of CO2 and cyclohexene epoxide.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Christian O. Blanco, Joshua Sims, Daniel L. Nascimento, Alexandre Y. Goudreault, Stephan N. Steinmann, Carine Michel, Deryn E. Fogg
Summary: Ruthenium catalysts for olefin metathesis are commonly thought to be water-tolerant, but evidence shows that even low concentrations of water can lead to catalyst decomposition and reduced yields. Fast-initiating catalysts are most affected, while the slow-initiating iodide and cyclic derivatives exhibit maximum water tolerance. Computational studies suggest that hydrogen bonding of water to the substrate can also impact the reaction.
Article
Chemistry, Applied
Adrian Sytniczuk, Pawel Malecki, Anna Kajetanowicz, Karol Grela
Summary: The activity of new indenylidene complexes with two unsymmetrical N-heterocyclic carbene (NHC) ligands was investigated. They were found to be effective in both straightforward olefin metathesis reactions and more demanding processes.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Anne V. Le, Biplab Rajbanshi, Raul F. Lobo, Peng Bai
Summary: In this study, DFT calculations were used to investigate the mechanisms of propene metathesis catalyzed by WOx/SiO2. The results showed that there are still many mechanisms of heterogeneous catalyzed metathesis reactions that are not well understood. The pseudo-Wittig mechanism was found to be the most favorable method for generating initial alkylidene active sites. The allylic and vinylic C-H activations are more difficult and require the reduction of surface sites to W(+4).
JOURNAL OF CATALYSIS
(2023)
Article
Crystallography
Fatin Nur Ain Abdul Rashid, Muhamad Zulfaqar Bacho, Alexandra M. Z. Slawin, Mohd Abdul Fatah Abdul Manan, Saiful Azmi Johari, Mohd Fazli Mohammat
Summary: The substance is triclinic with space group P (1) over bar (no. 2). The cell parameters are a = 7.9179(7) angstrom, b = 10.1982(9) angstrom, c = 10.4144(8) angstrom, alpha = 76.184(7) degrees, beta = 87.090 (7) degrees, gamma = 73.500(8) degrees. The volume of the unit cell is 782.86(12) angstrom(3), and there are 2 molecules in the lattice. The R-gt(F) value is 0.0458, and the wR(ref)(F-2) value is 0.1333. The temperature is 93 K.
ZEITSCHRIFT FUR KRISTALLOGRAPHIE-NEW CRYSTAL STRUCTURES
(2023)
Article
Crystallography
R. Alan Aitken, Alexander J. B. Nelson, Alexandra M. Z. Slawin, Dheirya K. Sonecha
Summary: Thirteen new crystal structures of cyclic NH carboximides have been determined and compared based on their intermolecular hydrogen bonding patterns. The structures include a new cyclobutane-fused succinimide, seven new simple bi- and tricyclic succinimides derived from Diels-Alder reactions, three methylated glutarimides, a morpholinedione and adipimide, and the first seven-membered ring NH carboximide to be characterized. The compounds were found to adopt ribbon structures, centrosymmetric dimers, and bonding between NH and a remote bridging ether oxygen. Halogen bonding was also observed in one case.
Article
Chemistry, Inorganic & Nuclear
Hang Liu, Hassan Hafeez, David B. Cordes, Alexandra M. Z. Slawin, Gavin Peters, Stephen L. Lee, Ifor D. W. Samuel, Finlay D. Morrison
Summary: In this work, a novel inorganic halide Cs10MnSb6Cl30 with a distinctive 10H perovskite polytype structure is reported. The Cs10MnSb6Cl30 has 30% B-site vacancies ordered at both corner-and face-sharing sites, resulting in a reduction of octahedral connectivity to 1D and enhanced photoluminescence. This study demonstrates the existence of the 10H perovskite structure in halides and the potential of vacancy rearrangements to tune the optical properties of perovskite polytypes.
INORGANIC CHEMISTRY
(2023)
Article
Crystallography
R. Alan Aitken, Alexandra M. Z. Slawin, Dheirya K. Sonecha
Summary: This paper reports the crystal structures of 2,5-dihydrothiophene 1,1-dioxide and 2,3-dihydrothiophene 1,1-dioxide, which show perfectly planar rings with expected bond lengths and angles. In contrast, the halogenated derivatives 3,3,4,4-tetrachlorotetrahydrothiophene 1,1-dioxide and 2,3-dibromotetrahydrothiophene 1,1-dioxide exhibit twisted conformations. The degree of planarity is compared with similar 5-membered ring cyclic sulfones, and the C-H...O hydrogen bonding patterns are discussed.
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY
(2023)
Article
Chemistry, Multidisciplinary
Tomas Matulaitis, Paloma L. dos Santos, Youichi Tsuchiya, David B. Cordes, Alexandra M. Z. Slawin, Chihaya Adachi, Ifor D. W. Samuel, Eli Zysman-Colman
Summary: Three new derivatives of 1,2,4,5-tetraphenylimidazole were synthesized and characterized. DMAC-TPI and PXZ-TPI showed low oscillator strength and low photoluminescence quantum yields, while PTZ-TPI exhibited room temperature phosphorescence by connecting a donor group to the N1 position.
Article
Chemistry, Inorganic & Nuclear
Lutao Zhang, Francesca A. Christie, Anna E. Tarcza, Helena G. Lancaster, Laurence J. Taylor, Michael Buhl, Olga L. Malkina, J. Derek Woollins, Cameron L. Carpenter-Warren, David B. Cordes, Alexandra M. Z. Slawin, Brian A. Chalmers, Petr Kilian
Summary: A series of peri-substituted acenaphthene-based phosphine selenoether bidentate ligands were synthesized and their properties in coordination with metals were investigated. The rigid ligands exhibited strong coupling effects and the coordination atoms were bridged by Lewis acidic motifs in the solid-state structures. Analysis of the NMR and X-ray diffraction data of the synthesized metal complexes provided insights into the interaction between the ligands and metals.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Stuart Burnett, Rochelle Ferns, David B. Cordes, Alexandra M. Z. Slawin, Tanja van Mourik, Andreas Stasch
Summary: This article reports on the different complexes obtained from the reactions of [(iPrDip)NacNac)Mg}(2)] with different reactants and reveals the structural characteristics of these complexes through experimental and computational studies.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Suman Mandal, Mitali Sarkar, Shanku Denrah, Arka Bagchi, Arunima Biswas, David B. Cordes, Alexandra M. Z. Slawin, Nitis Chandra Saha
Summary: A new pyrazole Schiff-base ligand and its two Ni(II) complexes have been synthesized and characterized. The complexes show promising catalytic and anticancer activities.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Crystallography
Saied M. Soliman, Ayman El-Faham, Assem Barakat, Alexandra M. Z. Slawin, John Derek Woollins, Morsy A. M. Abu-Youssef
Summary: Through X-ray crystallography, we synthesized and elucidated the structures of two IIB group complexes [Cd(DMPT)Cl-2] (6) and [Zn(DMPT)Cl-2] (7). Both complexes crystallized in the monoclinic crystal system, with different lattice parameters. Complex 6 exhibited a square pyramidal coordination environment, while complex 7 showed an intermediate between trigonal bipyramidal and square pyramidal coordination. Hirshfeld calculations revealed that hydrogen bonding interactions played a significant role in the supramolecular structure of both complexes.
Article
Chemistry, Multidisciplinary
Pagidi Sudhakar, Alexandra Slawin, Eli Zysman-Colman
Summary: This article reports the synthesis and optoelectronic characterization of several luminescent materials, and explains the changes in their luminescent properties in polymer films, revealing that some of these materials exhibit delayed fluorescence and reversible photoluminescent response.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sylwia Ostrowska, Pierre Arnaut, David J. Liptrot, Catherine S. J. Cazin, Steven P. Nolan
Summary: The synthesis, isolation, and full characterization of a new copper complex [Cu(IPr)(OC(H)(CF3)(2))] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) are reported. This copper(I) complex is a versatile synthon capable of activating various X-H bonds including C-H, N-H, and S-H bonds. [Cu(IPr)(OC(H)(CF3)(2))] was investigated as a pre-catalyst in several catalytic reactions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Alastair J. Nimmo, Jacqueline Bitai, Claire M. Young, Calum McLaughlin, Alexandra M. Z. Slawin, David B. Cordes, Andrew D. Smith
Summary: This study demonstrates an unusual reversible Michael addition reaction, using an isothiourea as a Lewis base catalyst, which produces stereoselective products. The basicity of the reaction conditions and the reactivity of the catalyst affect the selectivity of the products. By combining the reversible Michael addition with a crystallisation-induced diastereomer transformation, high yields and stereocontrol of the products can be achieved.
Article
Materials Science, Multidisciplinary
Ettore Crovini, Rama Dhali, Dianming Sun, Tomas Matulaitis, Thomas Comerford, Alexandra M. Z. Slawin, Cristina Sissa, Francesco Azzolin, Francesco Di Maiolo, Anna Painelli, Eli Zysman-Colman
Summary: We have studied the synthesis, optoelectronic properties, and theoretical analysis of DMAC-py-TRZ, a novel TADF emitter. The structural difference between DMAC-py-TRZ and DMAC-TRZ leads to significant changes in their steric interactions and photophysics. While the bent structure of DMAC-py-TRZ hinders TADF, emission can be observed from a relaxed orthogonal excited-state geometry. The presence of both conformers in amorphous matrices contributes to the efficiency of DMAC-py-TRZ devices through efficient energy transfer.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
John Marques dos Santos, Chin-Yiu Chan, Shi Tang, David Hall, Tomas Matulaitis, David B. Cordes, Alexandra M. Z. Slawin, Youichi Tsuchiya, Ludvig Edman, Chihaya Adachi, Yoann Olivier, Eli Zysman-Colman
Summary: Two novel p-extended amine/carbonyl-based multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters have been designed and synthesized. The two emitters are isomeric, composed of nine fused rings and show green-yellow emission. Sym-DiDiKTa and Asym-DiDiKTa possess tert-butyl groups distributed in a symmetrical and asymmetrical fashion, respectively, which significantly impact the single-crystal packing structure. The devices with Sym-DiDiKTa and Asym-DiDiKTa displayed electroluminescence maxima of 543 and 544 nm, and maximum external quantum efficiencies (EQE(max)) of 9.8% and 10.5%, respectively. The maximum EQE was further improved to 19.9% by employing a hyperfluorescence strategy. The LEC with Sym-DiDiKTa as the emitter showed a ?(EL) at 551 nm and FWHM of 60 nm with luminance of 300 cd m(-2) and a fast turn-on time of less than 2 s to 100 cd m(-2).
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Inorganic & Nuclear
Vladislav A. Voloshkin, Yaxu Liu, Marek Belis, Min Peng, Kristof Van Hecke, Catherine S. J. Cazin, Steven P. Nolan
Summary: The synthesis of novel phosphine palladium PEPPSI and dimer complexes bearing RuPhos, SPhos and XPhos phosphines is reported. The crystal structures of XPhos Pd PEPPSI with pyridine, SPhos Pd PEPPSI with 3-chloropyridine as throw-away ligands and the RuPhos palladium dimer were obtained and compared with previously reported congeners. The catalytic activity of these complexes was examined via a C-N coupling reaction, and it was found that RuPhos complex 2b showed the highest catalytic activity with 97% yield at a low catalyst loading. The addition of 3-pentanone significantly improved the yields of phosphine dimers and PEPPSI complexes when the reactions were performed in THF.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
