Review
Chemistry, Inorganic & Nuclear
Xinxin Hang, Yanfeng Bi
Summary: Thiacalix[4]arene-based molecular clusters are intriguing ligands with changeable conformations and excellent coordination ability, capable of constructing molecular-based functional materials with defined structures and various applications. Their combination with various molecular architectures shows special catalytic performances.
DALTON TRANSACTIONS
(2021)
Article
Biochemistry & Molecular Biology
Kamil Mamleev, Vaclav Eigner, Hana Dvorakova, Pavel Lhotak
Summary: Thiacalix[4]arene monosulfoxide 4 shows unique chemistry, with unprecedented derivatives in calixarene chemistry. It cannot be prepared by dealkylation, but forms a borate complex with a boron bound by neighboring phenolic oxygens and a sulfoxide group. Oxidation with Chloramine-T results in a complex oxathiane-based spiroheterocyclic part. X-ray analyses confirm the structures and propose feasible formation mechanisms, providing evidence of the distinction between thiacalixarene chemistry and classical CH2 analogues.
Article
Chemistry, Multidisciplinary
Shofiur Rahman, Hirotsugu Tomiyasu, Chuan-Zeng Wang, Paris E. Georghiou, Abdullah Alodhayb, Cameron L. Carpenter-Warren, Mark R. J. Elsegood, Simon J. Teat, Carl Redshaw, Takehiko Yamato
Summary: The synthesis and properties of three new heteroditopic receptors based on thiacalix[4]arenes in the 1,3-alternate conformation were reported. Among them, receptor 5c showed the most effective recognition ability towards the selected anions, as indicated by DFT computational determinations.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yanan Yu, Zhao Wang, Ziping Li, Xinxin Hang, Yanfeng Bi
Summary: Three cobalt-thiacalix[4]arene coordination clusters were synthesized using a solvothermal self-assembly method, featuring adenine-functionalized secondary building units. The structures exhibit different coordination modes and symmetries, formed by linking multiple basic units through ligand bridging.
Article
Chemistry, Inorganic & Nuclear
Wen-Lei Mu, Linlin Wu, Wei-Dong Yu, Xiao-Yi Yi, Jun Yan, Chao Liu
Summary: Accurate manipulation of ligands in clusters is challenging but important for controlling the properties and catalytic activity. In this study, two Cu(ii)-thiacalix[4]arene metallamacrocycles with different topologies were designed and synthesized, and the ligand substitution was successfully achieved. The effect of ligand tailoring on the electronic structure of clusters was revealed using theoretical calculations. The clusters showed promising catalytic activity for selective sulfide oxidation.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhi Wang, Hai-Feng Su, Li-Ping Zhang, Jian-Min Dou, Chen-Ho Tung, Di Sun, Lansun Zheng
Summary: This study reports a stepwise synthesis method using a thiacalix[4]arene-based metalloligand for the assembly of silver nanoclusters. The resulting nanoclusters are highly stable and exhibit low cytotoxicity and good activity against liver cancer cell lines.
Article
Multidisciplinary Sciences
Zhi Wang, Yan-Jie Zhu, Bao-Liang Han, Yi-Zhi Li, Chen-Ho Tung, Di Sun
Summary: The authors demonstrate the synthesis of two atomically precise silver nanoclusters (NCs) and showcase the thermal-induced structure transformation between the clusters during a temperature-dependent assembly process. Ag14 shows superior photothermal conversion performance, indicating its potential for remote laser ignition.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
D. Kortus, V. Eigner, P. Lhotak
Summary: The oxidation of 2,14-dithiacalix[4]arene led to the selective formation of S-spiro derivatives, indicating that the thiacalixarene fragment is more prone to spirocyclization than the calixarene one. Acid-induced rearrangement of the S-spiro compound resulted in a novel phenoxathiin-based calixarene macrocycle. The conformational preferences of these new inherently chiral macrocycles were studied using NMR spectroscopy, single-crystal X-ray analysis, and DFT calculations.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Meilin Wang, Yinjuan Guo, Guiyan Zhao, Baokuan Chen, Yanfeng Bi
Summary: Two new Ni8Mo8 bimetallic coordination clusters, Ni8PMo8 and Ni8Mo8, were synthesized and characterized. These two clusters can be directly loaded on carbon paper and used as working electrodes for glucose detection and oxidation, showing distinguishable performances. This work provides a better understanding of the structure-property relationships in using substituted polyoxometalates for electrochemical applications and is helpful for building functional materials based on calixarenes or polyoxometalates.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Applied
Mei Yu, Baichen Liu, Ju Guo, Fuyong Wu
Summary: In this paper, a novel thiacalix [4]arene probe (s2) with a colorimetric and fluorogenic chemosensor for efficient detection of Ag+ ions was synthesized. The probe exhibited highly sensitive ratiometric recognition to Ag+ ions and showed a wide dynamic concentration range with a detection limit of 7.6 x 10-9 M. The recognition mechanism between the probe and Ag+ ions was confirmed by various characterization techniques.
Article
Chemistry, Multidisciplinary
Zhi Wang, Fahri Alkan, Christine M. Aikens, Mohamedally Kurmoo, Zhen-Yi Zhang, Ke-Peng Song, Chen-Ho Tung, Di Sun
Summary: This study reports the single-crystal structure of the largest known mixed-valence silver nanoclusters protected by thiacalix[4]arenes and cyclohexanethiol. The structure consists of a metallic core with four concentric shells, surrounded by an organic skin. This work not only reveals the influence of macrocyclic ligands on the formation of large silver nanoclusters, but also provides a new structural archetype.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Engineering, Chemical
Tao Ge, Xiaowei Zhou, Liang Xu, Yan Sun, Cheng Yang, Yongpan Tian, Zhuo Zhao
Summary: In this study, the extraction performance and complexation mechanism of p-di-ethyl-amino-methylthiacalix[4]arene (L) towards Pt(IV) were investigated. The results indicated that L had excellent complexation ability towards Pt(IV) and could selectively extract it from a solution containing multiple competing ions.
MINERALS ENGINEERING
(2024)
Article
Chemistry, Inorganic & Nuclear
Jie Li, Peng Du, Ying-Ying Liu, Jian-Fang Ma
Summary: The self-assembly of polyoxometalates, Ni(ii)/Ag(I) cations and tetra-[5-(mercapto)-1-methyltetrazole]-thiacalix[4]arene yielded three inorganic-organic hybrids with different structures and catalytic properties. Hybrid (1) and Hybrid (3) showed excellent heterogeneous catalytic activity in oxidation desulfurization reactions.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Shang-Qian Li, Lin-Fang Dai, Yi-Qi Tian, Yi-Xiao Yi, Jun Yan, Chao Liu
Summary: In this study, a large polymolybdate-templated {Ag49Mo16} cluster protected by six thiacalix[4]arene (TC4A) molecules was synthesized. Structural analysis revealed that the {Ag49Mo16} cluster is assembled by inserting a [Mo6O22](8-) cluster into a [Ag49Mo10@(TC4A)(6)] cage. The solution stability and photoelectric properties of {Ag49Mo16} were discussed, and its electrocatalytic CO2 reduction application showed promising results with a CO faradaic efficiency (FE) of 44.75% at -0.8 V (vs. RHE).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhao Wang, Meilin Wang, Kai He, Xinxin Hang, Yanfeng Bi
Summary: Metal sulfides are promising electrodes for electrochemical energy storage. In this study, Co9S8 nanoparticles anchored on a carbon matrix were prepared from precursor sources. The smaller size and larger BET surface area of Co9S8-2@CN nanoparticles improve electrical conductivity and charge transport pathways, leading to superior electrochemical performance compared to Co9S8-1@CN.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Physical
Tahere Kondori, Niloufar Akbarzadeh-T, Mahboubeh Fazli, Behrouz Mir, Michal Dusek, Vaclav Eigner
Summary: A novel Schiff base ligand and its copper complex showed antibacterial activities against various bacterial strains, with the complex demonstrating stronger activity against gram-positive bacteria.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Organic
Martin Tlusty, Vaclav Eigner, Pavel Lhotak
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Anastasia Surina, Vaclav Eigner, Martin Krupicka, Pavel Lhotak
Summary: Desymmetrization of persubstituted calix[4]arenes can yield distally disubstituted derivatives that are difficult to obtain by other methods. This study demonstrates the usefulness of this method and provides a possible explanation for the unexpected selectivity, using a combination of synthetic and theoretical approaches.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Marketa Tichotova, Tomas Landovsky, Jan Lang, Sharon Jeziorowski, Volker Schmidts, Michal Kohout, Martin Babor, Pavel Lhotak, Christina M. Thiele, Hana Dvorakova
Summary: By using polyglutamates with different side-chain moieties (PBLG and PBPMLG) as alignment media, we achieved enantiodiscrimination of inherently chiral compounds for the first time. The experimental results not only provided more accurate structural information, but also revealed the conformational preferences and chiral alignment differences of phenoxathiin-based thiacalix[4]arenes in solution.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Martin Tlusty, Vaclav Eigner, Hana Dvorakova, Pavel Lhotak
Summary: This study reports an easy method to prepare inherently chiral calixquinoline compounds by the reaction of aldehydes with aminocalix[4]arenes under acidic conditions. These compounds are capable of forming complexes with quaternary ammonium salts with different stoichiometries and demonstrated enantioselective complexation ability with chiral N-methylammonium salts.
Article
Chemistry, Organic
Dorota Konvalinkova, Frantisek Dolnicek, Michaela Hovorkova, Jakub Cerveny, Ondrej Kundrat, Helena Pelantova, Lucie Petraskova, Josef Cvacka, Margarita Faizulina, Beena Varghese, Petr Kovaricek, Vladimir Kren, Pavel Lhotak, Pavla Bojarova
Summary: This study reports the synthesis of potential galectin ligands based on the calix[4]arene core and investigates the influence of linkers and core structure on their affinity. Competitive assays using ELISA and biolayer interferometry demonstrate significant differences in affinity based on linker length and the position of the triazole unit. Atomic force microscopy detects the formation of supramolecular clusters.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Kamil Mamleev, Vaclav Eigner, Hana Dvorakova, Pavel Lhotak
Summary: Thiacalix[4]arene monosulfoxide 4 shows unique chemistry, with unprecedented derivatives in calixarene chemistry. It cannot be prepared by dealkylation, but forms a borate complex with a boron bound by neighboring phenolic oxygens and a sulfoxide group. Oxidation with Chloramine-T results in a complex oxathiane-based spiroheterocyclic part. X-ray analyses confirm the structures and propose feasible formation mechanisms, providing evidence of the distinction between thiacalixarene chemistry and classical CH2 analogues.
Article
Chemistry, Organic
N. Broftova, T. Landovsky, H. Dvorakova, V. Eigner, M. Krupicka, P. Lhotak
Summary: A phenoxathiin-based macrocycle, accessible from thiacalix[4]arene in two steps, is found to be inherently chiral. During transformations, oxidized derivatives with one sulfoxide group and three sulfonyl groups show unexpected stereochemical preferences. The sulfoxide moiety always points out of the cavity (S=O out), and the opposite (S=O in) configuration is never obtained by direct oxidation. Achieving full oxidation to sulfone requires photochemical inversion of the sulfoxide group prior to the final oxidation. The stereomutation of the sulfoxide group in the thiacalixarene series is studied using experimental (NMR and single crystal X-ray analysis) and theoretical (DFT) approaches.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Review
Chemistry, Organic
Pavel Lhotak
Summary: Calixarenes are popular building blocks in supramolecular chemistry due to their almost infinite derivatization possibilities. Meta substitution of the aromatic skeleton in calixarenes is a synthetic challenge that leads to inherent chirality and the synthesis of derivatives with previously undescribed topology.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
M. Tlusty, V Eigner, H. Dvorakova, P. Lhotak
Summary: The amine-bridged calix[4]arene can be synthesized by introducing an azide group into the macrocyclic skeleton and then undergoing thermal decomposition. Alkylation reactions for further modification of the amine bridge were problematic, but acylation reactions proceeded smoothly. The compounds displayed unusual dynamic behavior due to restricted rotation around the amide C-N bond, which led to desymmetrization in the H-1 NMR spectra at low temperatures. Substituting the proximal aromatic units of the acylated amine-bridged calix[4]arene with bromine atoms resulted in inherently chiral systems with hindered rotation at room temperature.
NEW JOURNAL OF CHEMISTRY
(2022)
