Article
Polymer Science
Salvatore Impemba, Gabriele Manca, Irene Tozio, Stefano Milione
Summary: In this study, new zinc catalysts were developed using thioether-amide ligands for the ring-opening polymerization of cyclic esters. Experimental and theoretical studies provided insights into the parameters that influence catalytic activity. The catalysts exhibited high activity in the polymerization of rac-beta-butyrolactone and showed agreement with expected results in terms of molecular weight and polydispersity index.
Review
Chemistry, Multidisciplinary
An Sofie Narmon, Christian A. M. R. van Slagmaat, Stefaan M. A. De Wildeman, Michiel Dusselier
Summary: As the concern for environmental effects of plastics grows, the industry is turning towards more sustainable polymers, such as polythioesters (PTEs). PTEs have gained attention for their enhanced properties and high sustainability potential due to the introduction of sulfur atoms and their inherent susceptibility to degradation. This review critically discusses the potential sustainability of PTEs obtained through ring-opening polymerization of thio(no)lactones, including their industrial perspective and comparison to aliphatic polyesters (PEs).
Article
Chemistry, Physical
Jonathan E. Chellali, Alexander K. Alverson, Jerome R. Robinson
Summary: This study reports a new class of Zn catalysts that exhibit high activity and stability in the ring-opening polymerization of lactide. Mechanistic studies revealed a quantitative structure-function relationship between the steric profile of the catalyst's reaction site and its activity, providing important insights for the design of homogeneous catalysts.
Article
Polymer Science
Kana Takebayashi, Arihiro Kanazawa, Sadahito Aoshima
Summary: The cationic ring-opening copolymerization of cyclic acetals and 1,3-dioxolan-4-ones (DOLOs) was investigated, with a focus on understanding the polymerization mechanisms. The copolymerization of 1,3-dioxepane and 5-methyl-1,3-dioxolan-4-one successfully occurred using CF3SO3H as a catalyst, resulting in high molecular weight copolymers. NMR spectrometry and electrospray ionization mass spectrometry were used to analyze the detailed structure of the copolymers, which indicated that the copolymerization proceeds through an activated monomer mechanism involving the reaction of a hydroxy group and a proton-attached DOLO. Acid-catalyzed transacetalization reactions also likely occurred during the copolymerization process.
Article
Chemistry, Physical
Rou-Rong Su, Prasanna Kumar Ganta, Che-An Cheng, Yu-Ting Hu, Yung-Chi Chang, Chun-Juei Chang, Shangwu Ding, Hsuan-Ying Chen, Kuo-Hui Wu
Summary: A series of zinc complexes with ethyl salicylates were synthesized and their catalytic activity in the polymerization of epsilon-caprolactone and L-lactide was investigated. Ligands with substituents at the ortho position of phenolates promoted the catalytic activity in CL polymerization, while ligands with electron-donating substituents promoted the activity in LA polymerization. Density functional theory calculations revealed the mechanism behind the polymerization.
MOLECULAR CATALYSIS
(2023)
Article
Polymer Science
Balazs Pasztoi, Tobias M. Trotschler, Akos Szabo, Benjamin Kerscher, Heikki Tenhu, Rolf Muelhaupt, Bela Ivan
Summary: Cationic ring-opening polymerization of EtOx in BTF and other solvents shows similar kinetics, with BTF offering the highest polymerization rates and conversions; The Arrhenius parameters indicate relatively high activation energy in BTF, but a compensation effect is observed between activation energies and frequency factors in various solvents.
Article
Polymer Science
Rawan Omar, Muneer Shaik, Chloe Griggs, Jevin D. Jensen, Robert Boyd, Nuri Oncel, Dean C. Webster, Guodong Du
Summary: This study successfully synthesized a series of star-shaped poly (beta-hydroxybutyrates) (PHBs) through ring-opening polymerization of cyclic esters using multifunctional initiators, and characterized their structure and properties through various techniques. The thermal properties of star-shaped PHBs can be modified by changing the arm number and arm length, while the wetting behavior of star-shaped PHBs is influenced by the number of arms.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Xun Zhang, Pan Sun, Yu Jiang, Saihu Liao
Summary: In this study, an efficient metal-free organic catalytic system using PADIs as catalysts has been developed for the ring-opening polymerization of ε-caprolactone. The system allows for the synthesis of poly(ε-caprolactone) with predictable molecular weight and narrow dispersity under mild conditions.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Hong Zhang, Xiaoyun Geng, Ziqiang Li, Ying Peng, Lijuan Wang, Pengjiao Chen
Summary: A series of N-alkyl-beta-ketoiminate monozinc complexes were synthesized and characterized. The structures of these complexes were determined by single-crystal X-ray diffraction, revealing a distorted tetrahedral geometry around the zinc center. These bis(beta-ketoiminate) zinc complexes exhibited high activity towards the ring-opening polymerization of rac-lactide in the absence of alcohol.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Zixuan Xu, Zhaoyu Wang, Yanyun Zhang, Xiaokang Yao, Meijuan Ding, Huifang Shi, Zhongfu An
Summary: A novel series of neutral photo-acid generators (PAGs) based on carbazole derivatives are presented, which show the highest quantum yield (over 85%) among Bronsted PAGs under UV irradiation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Polymer Science
Zan Yang, Wenpei Xiao, Xun Zhang, Saihu Liao
Summary: This study reports an organocatalytic degenerate chain transfer (DCT) polymerization of vinyl ethers with temporal control under visible light. By using a bisphosphonium salt as the photocatalyst and thioacetal as the chain transfer agent, poly(vinyl ether)s with good molecular weight control and narrow molecular weight distributions can be obtained. The resulting polymers show high chain-end fidelity, allowing further chain extension and functionalization to synthesize block copolymers and end-functionalized polymers. The stability and efficiency of the catalyst enable a strict temporal control over polymer chain growth at high monomer conversion for a long dark period.
Article
Polymer Science
Tobias A. Bauer, Christian Muhl, Dieter Schollmeyer, Matthias Barz
Summary: The use of racemic mixtures of NCAs can improve reaction rates and monomer conversion, the controlled living nature of polypeptide ring-opening polymerization enables the synthesis of high DP polypeptides and triblock copolymers with symmetric molecular weight distributions through sequential monomer addition.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Polymer Science
Moritz Koehler, Philipp Rinke, Kevin Fiederling, Helmar Goerls, Nico Ueberschaar, Felix Helmut Schacher, Robert Kretschmer
Summary: Novel dinuclear bis(beta-diketiminate) complexes with flexible alkylene bridging groups and biocompatible zinc centers were introduced for the catalytic ring-opening polymerization (ROP) of caprolactones. These complexes exhibited improved control over polymerization in comparison to a mononuclear counterpart, especially in the presence of benzyl alcohol as an initiator.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Hui Li, Jerome Ollivier, Sophie M. Guillaume, Jean-Francois Carpentier
Summary: This study reports the first chemical synthesis of poly(3-thiobutyrolactone) (P3TB) through ring-opening polymerization. The reactions proceed rapidly in the presence of various metal-based catalysts, and high selectivity can be achieved by manipulating reaction conditions and catalyst systems. The topology and stereochemistry of the resulting polymer have been characterized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Tiansi Xin, Michael B. Geeson, Hui Zhu, Zheng-Wang Qu, Stefan Grimme, Christopher C. Cummins
Summary: The structural characterization and scalable preparation of iron-phosphido complex FpP(Bu-t)(F) and its precursor FpP(Bu-t)(Cl) are reported, along with their relevance in organoiron catalytic cycle. The discovery of a more efficient catalytic system and successful synthesis of phosphirane compounds are also discussed.
Article
Chemistry, Multidisciplinary
Jonas F. Schlagintweit, Philipp J. Altmann, Alexander D. Boeth, Benjamin J. Hofmann, Christian Jandl, Clemens Kaussler, Linda Nguyen, Robert M. Reich, Alexander Poethig, Fritz E. Kuehn
Summary: The first dicobalt(III) mu(2)-peroxo N-heterocyclic carbene (NHC) complex was reported, showing the ability to be generated from air and cleaved into a Co-III acetate complex upon addition of acetic acid. Experimental and theoretical studies suggest a nucleophilic nature of the dicobalt(III) mu(2)-peroxo complex.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Joao Guilherme M. de Carvalho, Roland A. Fischer, Alexander Poethig
Summary: In this study, a dipyridyl-substituted anthraquinone was incorporated into crystalline coordination networks, with the oxidation state of the organic linker selectively controlled and maintained in the solid state through hydrogen bonding. The anthraquinone-anthrahydroquinone redox pair was shown to be reversibly switched even after incorporation in the solid state, with the formation of hydrogen peroxide from molecular oxygen during the oxidation process.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Salvatore Baldino, Steven Giboulot, Denise Lovison, Hans Guenter Nedden, Alexander Poethig, Antonio Zanotti-Gerosa, Daniele Zuccaccia, Maurizio Ballico, Walter Baratta
Summary: A series of rhodium complexes have been synthesized and their isomerization reactions in methanol have been studied, using different nitrogen ligands and diphosphine ligands in the synthesis process.
Article
Chemistry, Multidisciplinary
Sebastian Koller, Philippe Klein, Katja Reinhardt, Lukas Ochmann, Antonia Seitz, Christian Jandl, Alexander Poethig, Lukas Hintermann
Summary: A group of transition-metal catalyzed hydrogen moving reactions have been studied, with synthetic access routes established for a toolbox of structurally varied ligands and pincer complexes. Asymmetrically modified versions of established catalysts have been prepared for research towards asymmetric catalytic hydrogen moving reactions, showing potential in various model reactions such as transfer hydrogenation and alkene isomerization.
HELVETICA CHIMICA ACTA
(2021)
Article
Chemistry, Inorganic & Nuclear
Margit Aust, Anna J. Herold, Lukas Niederegger, Christian Schneider, David C. Mayer, Markus Drees, Julien Warnan, Alexander Poethig, Roland A. Fischer
Summary: Benzene-1,3,5-tri(dithiocarboxylate) is a potential multidentate ligand in coordination chemistry, capable of forming both discrete metal complexes and coordination polymers. Its versatile coordination behavior was demonstrated through synthesis of trinuclear Cu(I) and hexanuclear Mo(II)(2) complexes, making it a promising tritopic linker for functional coordination polymers.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Katja Reinhardt, Sebastian Koller, Philippe Klein, Corvin Lossin, Julia Gatzka, Philipp J. Altmann, Alexander Poethig, Lukas Hintermann
Summary: The study focuses on the attachment of di(1R)-menthylphosphino fragments to molecular scaffolds to create homochiral, bulky phosphine ligands for potential applications in coordination chemistry and transition-metal catalysis. Various transformations and reactions involving dimenthylphosphine P-oxide are explored, leading to the synthesis of new ligands and complexes with specific reactivity profiles due to the presence of menthyl groups. This approach shows promise for use in model palladium-catalyzed coupling reactions, with ligand 22 exhibiting high enantioselectivity in a specific biaryl-forming reaction.
Article
Chemistry, Physical
Sebastian J. Weishaeupl, Yang Cui, Simon N. Deger, Hamad Syed, Aleksandr Ovsianikov, Juergen Hauer, Alexander Poethig, Roland A. Fischer
Summary: Multiphoton absorption (MPA) is of great interest in modern materials research, and metal-organic frameworks and coordination polymers (CPs) are potential materials to overcome the limitations of commonly used chromophore molecules. This article reports the synthesis and characterization of three new highly MPA-active CPs, and demonstrates their large two-photon absorption cross-sections, which are among the highest reported for CPs to date.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Joao Guilherme M. de Carvalho, Korbinian Geisser, Sebastian J. Weishaeupl, Roland A. Fischer, Alexander Poethig
Summary: A tetratopic bis(diphenylamino)anthraquinone linker is presented in this study. Its physicochemical and emissive properties are evaluated, and it successfully coordinates alkaline earth metals to form four new reported metal-organic frameworks (MOFs). The catalytic behavior of the ligand and the MOF materials towards the photooxidation of sulfides is also described.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Medicinal
Valeria Scalcon, Riccardo Bonsignore, Jana Aupic, Sophie R. Thomas, Alessandra Folda, Alexandra A. Heidecker, Alexander Pothig, Alessandra Magistrato, Angela Casini, Maria Pia Rigobello
Summary: Two new hybrid metallodrugs of Au(III)(AuTAML)and Cu(II) (CuTAML) were designed to synergize the anticancer activity of both the metal centerand the organic ligand. These drugs showed antiproliferative effects against breast cancer cells and retained binding activity to estrogen receptor (ERα). Furthermore, they exhibited different reactivities and cytotoxic potencies, but displayed a capacity to induce mitochondrial damage.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Denise Lovison, Tobias Berghausen, Sophie R. Thomas, Jonathan Robson, Markus Drees, Christian Jandl, Alexander Poethig, Patrick Mollik, Dominik P. Halter, Walter Baratta, Angela Casini
Summary: In this study, water-soluble organometallic Ru(II) complexes were synthesized and found to act as anticancer agents by catalyzing transfer hydrogenation reactions with biomolecules. The structure-activity relationship and reaction mechanism were investigated, and the compounds were also tested for their anticancer activity in vitro.
Article
Multidisciplinary Sciences
Shangpu Liu, Mikael Kepenekian, Stanislav Bodnar, Sascha Feldmann, Markus W. Heindl, Natalie Fehn, Jonathan Zerhoch, Andrii Shcherbakov, Alexander Poethig, Yang Li, Ulrich W. Paetzold, Aras Kartouzian, Ian D. Sharp, Claudine Katan, Jacky Even, Felix Deschler
Summary: This study reveals the unique photoluminescence properties of hybrid perovskite semiconductor materials, which can achieve high luminescence yields and circularly polarized photoluminescence at room temperature. The excellent photoluminescence performance is attributed to the suppression of nonradiative loss channels and the high rates of radiative recombination. These findings pave the way for high-performance solution-processed photonic systems and chiral-spintronic logic at room temperature.
Article
Chemistry, Inorganic & Nuclear
Yanyan Zhi, Ziwei Feng, Tanisha Mehreen, Xiaoyuan Liu, Kirsty Gardner, Xiangping Li, Bai-Ou Guan, Lijuan Zhang, Sergey Vagin, Bernhard Rieger, Alkiviathes Meldrum
Summary: In this study, the two-photon fluorescence (TPF) of conjugated polymer (CP) microspheres with diameters up to tens of micrometers was investigated. Two types of polymers emitting in violet and red were synthesized and characterized. It was found that under femtosecond infrared excitation, both types of microspheres exhibited strong TPF, with the red-fluorescent microspheres showing a much stronger TPF compared to the violet-fluorescent microspheres. The enhanced hyperpolarizability associated with intermolecular interactions in the polymer solid was attributed to the excellent TPF performance of the red-fluorescent microspheres, suggesting a potential route for designing CP microspheres with superior TPF properties for sensing or imaging applications.
Review
Materials Science, Multidisciplinary
Sebastian J. Weishaeupl, David C. Mayer, Yang Cui, Pushpendra Kumar, Harald Oberhofer, Roland A. Fischer, Jurgen Hauer, Alexander Poethig
Summary: This review presents recent advances in metal-organic frameworks (MOFs) and coordination polymers (CPs) regarding their response properties to multiphoton absorption (MPA). It covers the theoretical background of MPA absorbing linker molecules, the effect of excitonic coupling within a rigid framework assembly, and compares different scanning and non-scanning measurement techniques for two-photon absorption (TPA) spectroscopy. Additionally, it comprehensively presents the latest progress of linker-based MPA materials and their relationship with framework structure and MPA cross section.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Inorganic & Nuclear
Brech Aikman, Riccardo Bonsignore, Ben Woods, Daniel Doellerer, Riccardo Scotti, Claudia Schmidt, Alexandra A. Heidecker, Alexander Poethig, Edward J. Sayers, Arwyn T. Jones, Angela Casini
Summary: Research focused on designing new metallosupramolecular structures for drug delivery. Two self-assembled metal cages capable of encapsulating anticancer drugs have been synthesized and characterized. The stability and intracellular localization of these structures have been confirmed, and their antiproliferative activity has been investigated.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Shengyang Guan, Thomas Pickl, Christian Jandl, Leon Schuchmann, Xiaoyu Zhou, Philipp J. Altmann, Alexander Pothig
Summary: Triazolate-based pillarplexes are a new type of supramolecular organometallic complexes with tubular pores, using a hybrid imidazolium/triazole cyclophane as a ligand precursor. These new pillarplexes show similarities to previously reported pyrazolate-based congeners, but exhibit unprecedented shape-adaptive behavior in the solid-state for the Au(i) complex, rationalized by DFT calculations. Additionally, complementary hydrogen bonding between cationic complexes is observed, demonstrating that rim modification not only modulates cavity flexibility, but also introduces further functionality into the SOC.
ORGANIC CHEMISTRY FRONTIERS
(2021)
