Article
Chemistry, Inorganic & Nuclear
Firasat Hussain, Imran Khan, Vivek Das
Summary: The catalytic activity of tetrameric lanthanide-substituted phospho, germano, and silicotungstate compounds was investigated for the oxidation of alcohol derivatives. The study found that the lanthanide-substituted phosphotungstates exhibited better catalytic activity compared to the silico and germanotungstate analogues. The reaction was carried out in an environmentally friendly solvent (water) in the presence of a green oxidant (H2O2). The recovered catalysts were characterized using FT-IR spectroscopy and powder X-ray diffraction. The catalysts showed stability and could be reused with only a slight decrease in catalytic activity after five consecutive cycles.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Physical
Anda Ioana Gratiela Petrehele, Narcis Duteanu, Mona Claudia Morgovan, Sanda Monica Filip, Stefania Ciocan, Eleonora Marian
Summary: Five new complexes with metal cations (Mn2+, Fe3+, Co2+, Ni2+, and Cu2+) of monolacunary Keggin monovanado-deca-tungstophosphate, K-8[PVW10O39]center dot 15H(2)O, have been successfully synthesized. The molar ratio of the combination between metal cations and K-8[PVW10O39]center dot 15H(2)O was determined to be 1:1, and their general molecular formulas were found to be K-n[MPVW10O39(H2O)]center dot xH(2)O (n = 5 for M = Fe3+ and n = 6 for M = Mn2+, Co2+, Ni2+, and Cu2+). The optimal conditions for the synthesis of these complexes have been determined, and various characterization methods have been used to confirm their compositions, structures, and properties.
Article
Chemistry, Multidisciplinary
Minghui Zhu, Shicheng Han, Junrui Liu, Mengjin Tan, Wei Wang, Kosuke Suzuki, Panchao Yin, Debin Xia, Xikui Fang
Summary: This study reports the formation of giant {Mo126W30} polyoxometalate cages templated by pi-conjugated planar ligands, with inorganic shells containing arrays of stacked aromatic carboxylates stabilized by multiple pi-pi interactions. NMR data confirmed the stability of the cages in solution, and showed that the inner aromatic templates can be postsynthetically replaced by selected aliphatic dicarboxylates. This paves the way for endo-functionalization and exploration of reactivities within the cage cavities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Eduard Garrido Ribo, Nicola L. Bell, De-Liang Long, Leroy Cronin
Summary: The study demonstrates the possibility of greater structural diversity in the assembly of nanoscale POM clusters, presenting new classes of highly reduced mixed-valence POMs. This includes the supercube structure of {Mo-64} and the pentagonal star topology of {Mo-70}, with potential applications in lanthanide enrichment through differences in selectivity in the self-assembly of polyoxometalates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Timothy M. Swager
Summary: Bottom-up materials design using liquid crystals allows for the creation of materials with dynamic properties and directional order through cooperative interactions and the application of electric/magnetic fields. This is achieved through the thermal excitation of side chains and the anisotropic attractions between mesogenic cores in the liquid crystal state. Unconventional mesogens offer opportunities for the creation of responsive molecular assemblies with optical, electronic, or magnetic activity.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Nanoscience & Nanotechnology
Tsukasa Iwano, Kota Shitamatsu, Naoki Ogiwara, Masanari Okuno, Yuji Kikukawa, Satoru Ikemoto, Sora Shirai, Satoshi Muratsugu, Paul G. Waddell, R. John Errington, Masahiro Sadakane, Sayaka Uchida
Summary: A novel hybrid material composed of a Preyssler-type polyoxometalate functionalized with a 9-coordinate Eu3+ and poly(allylamine) has been synthesized, exhibiting ultrahigh proton conductivity and robust crystalline structure. The approach of strengthening and extending hydrogen-bonding network enables the material to maintain high conductivity even under lower humidity conditions.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Jan-Christian Raabe, Jakob Albert, Maximilian J. Poller
Summary: This study investigates the possibility of adjusting the RedOx activity of polyoxometalate catalysts by introducing an additional RedOx-active element. Keggin-type polyoxometalates (POMs) with multiple different elements are synthesized, and their structures and characteristics are comprehensively characterized using various analytical methods.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Tuba Iftikhar, Natalya V. Izarova, Jan van Leusen, Paul Kogerler
Summary: A family of solution-stable polyanions containing single lanthanide(III) or yttrium(III) ions in a rare trigonal prismatic environment were synthesized by exploiting the reactivity of an organophosphonate-functionalized precursor. The resulting Dy, Ho, Er, and Yb derivatives exhibit slow magnetization relaxation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Danielle C. Hutchison, Rachelle M. Smith, May Nyman
Summary: The Keggin cluster topology, initially discovered in tungsten polyoxometalates about a century ago, is widely represented across the periodic table. Alkyltin Keggin clusters, unique in favoring rare beta and gamma rotational isomers, show lability and ready exchange of ligands under the influence of residual water in polar solvents. Room temperature and heated solutions of beta,gamma-NaSn12 exhibit all five Keggin rotational isomers simultaneously, providing unique insight into their stabilization, isolation, and exchange.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Nanoscience & Nanotechnology
Shulin Li, Shanshan Zhang, Ning Feng, Na Zhang, Yu Zhu, Yuhao Liu, Wenjuan Wang, Xia Xin
Summary: The construction of controllable chiroptical supramolecular luminescence systems using chiral metal nanoclusters (NCs) is important for developing intelligent chiral luminescence materials and understanding chirality-switching phenomena. In this study, a supramolecular luminescent hydrogel was constructed using chiral glutathione-stabilized copper NCs (G-SH-Cu NCs), achiral branched polyethyleneimine (PEI), and polyoxometalates (EuW10). The addition of PEI induced chiral inversion in the hydrogel, while further addition of EuW10 enhanced the luminescence and recovered the chiroptical properties. The mechanisms behind the chiral inversion and recovery were attributed to hydrogen bonding and electrostatic interactions. This work provides a feasible strategy for modulating the chiral inversion behavior of metal NCs and offers potential applications for chiroptical materials.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Takaya Fujie, Takeshi Yamamoto, Michinori Suginome
Summary: A single-handed poly(quinoxaline-2,3-diyl) (PQX) has been discovered as a new type of chiral shift reagent (CSR) for determining enantiomeric ratio by NMR spectroscopy. Without specific binding site, PQX interacts nonbondingly with chiral analytes, resulting in significant shift of NMR chemical shift and enabling quantification of enantiomeric ratios. This new CSR offers advantages such as wide analyte scope, including ethers, haloalkanes, and alkanes, easy tunability of chemical shifts with temperature, and erasability of proton signals due to short T-2 relaxation of the macromolecular scaffold.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Engineering, Electrical & Electronic
Sergey P. Babailov, Marina A. Polovkova, Gayane A. Kirakosyan, Alexander G. Martynov, Evgeny N. Zapolotsky, Yulia G. Gorbunova
Summary: This paper demonstrates the thermosensing properties of binuclear triple-decker terbium(III) and dysprosium(III) complexes at physiological temperature range, with terbium-containing complex showing the highest sensitivity among published complexes in nonpolar solutions. The significant impact of Curie-spin contribution on paramagnetic spin-spin relaxation rate enhancement with pronounced temperature dependence is also highlighted.
SENSORS AND ACTUATORS A-PHYSICAL
(2021)
Article
Chemistry, Physical
Stefanie Wesinger, Matthias Mendt, Jakob Albert
Summary: Alcoholic solvents, especially methanol, activate heteropolyacids in homogeneously catalyzing glucose transformation reactions, resulting in high carbon efficiency. Through spectroscopic tools, it has been proven that the complex in methanolic solution plays a key role in the selectivity shift of the transformation reaction.
Article
Chemistry, Inorganic & Nuclear
Imran Khan, Vivek Das, Anne-Lucie Teillout, Israel-Martyr Mbomekalle, Pedro de Oliveira, Subash Chandra Sahoo, Firasat Hussain
Summary: A series of nanoclusters with different lanthanides have been synthesized, characterized, and shown to be efficient catalysts for the oxidation of thioethers using H2O2. The catalyst can be recovered with minimal loss in activity even after multiple reaction cycles.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Perrine M. R. Wingering, Silvia Hohnstein, Felix Kraemer, Melina E. A. Dilanas, Cristina Ruiz-Martinez, Ignacio Fernandez, Frank Breher
Summary: The synthesis and characterization of rare earth element complexes (Ln=Y, La, Sm, Lu, Ce) of several podant & kappa;N-6-coordinating ligands were conducted. The structural properties of the complexes were studied using X-ray diffraction and advanced NMR methods. To evaluate the donor capabilities of the ligands, cyclic voltammetry, absorption experiments, and Y-89 NMR chemical shift analysis were performed. Quantum chemical calculations were also used to support the experimental findings. Furthermore, coordination competition studies were carried out using H-1 and P-31 NMR spectroscopy to investigate the correlation with donor properties and selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biophysics
Nassif Chahin, Laura A. Uribe, Ahmed M. Debela, Serge Thorimbert, Bernold Hasenknopf, Mayreli Ortiz, Ioannis Katakis, Ciara K. O'Sullivan
BIOSENSORS & BIOELECTRONICS
(2018)
Article
Chemistry, Multidisciplinary
Mayreli Ortiz, Ahmed M. Debela, Christophe Methivier, Serge Thorimbert, Bernold Hasenknopf, Ciara K. O'Sullivan
CHEMISTRY-A EUROPEAN JOURNAL
(2018)
Review
Chemistry, Organic
Kevin Passador, Serge Thorimbert, Candice Botuha
SYNTHESIS-STUTTGART
(2019)
Article
Chemistry, Organic
Anissa Beghennou, Kevin Passador, Anthony Passador, Vincent Corce, Serge Thorimbert, Candice Botuha
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Liang Chang, Nathalie Fischer-Durand, Geoffrey Gontard, Benoit Bertrand, Serge Thorimbert, Luc Dechoux
Summary: A novel dearomatization reaction for nitrogen-containing heterocycles was developed, utilizing biorenewable methyl coumalate as an efficient partner under solvent-free conditions. This reaction successfully converted nine types of basic aromatic rings into their pyrido[1,2-a] fused derivatives, with good to excellent yields. The fluorescence properties of the products were harnessed for conjugating fluorescent tags to bovine serum albumin (BSA) and immunoglobulin G.
Article
Chemistry, Organic
Sawsen Cherraben, Jeremy Scelle, Bernold Hasenknopf, Guillaume Vives, Matthieu Sollogoub
Summary: A family of cyclodextrins functionalized with different numbers of amines can control the rate of their threading and dethreading on a molecular axle based on pH and substitution pattern. The uniqueness of this system lies in the ability to directly control the switch rate by operating the stimulus on the macrocycle.
Article
Chemistry, Multidisciplinary
Jeremy Scelle, Hugo Vervoitte, Laurent Bouteiller, Lise-Marie Chamoreau, Matthieu Sollogoub, Guillaume Vives, Bernold Hasenknopf
Summary: The encapsulation of guests in a confined space can lead to unusual conformations and reactivities. This study focuses on the effect of a cyclodextrin (CD) dimer cavity on the conformation of alpha,omega-alkyl-diphosphate axles in pseudorotaxane architectures. Results show that in both solid and solution states, the CD can compress the alkyl chain, resulting in conformational changes.
Article
Chemistry, Organic
Alexander Mamontov, Liang Chang, Heloise Dossmann, Benoit Bertrand, Luc Dechoux, Serge Thorimbert
Summary: In this study, commercially available Fe(TTP)Cl catalyst was used to catalyze the three-component dearomative formal cycloaddition reactions between pyridines, diazo compounds, and coumalates at room temperature. Diversely substituted annelated seven-membered N-heterocycles could be synthesized in less than 10 minutes with high efficiency. The study also demonstrated the successful substitution of benzimidazoles for pyridines in this reaction.
Article
Materials Science, Multidisciplinary
Anthony Nina-Diogo, Benoit Bertrand, Serge Thorimbert, Geoffrey Gontard, Sehr Nassem-Kahn, Andrea Echeverri, Julia Contreras-Garcia, Clemence Allain, Gilles Lemercier, Eleonora Luppi, Candice Botuha
Summary: This report presents the design, synthesis, and photophysical study of two new series of promising fluorescent trisubstituted triazoles, PyOHTr and PyCOTr. The PyOHTr molecules were found to exhibit an excited state intramolecular proton transfer (ESIPT) fluorescence mechanism through ab initio theoretical calculations. These fluorescent dyes possess unique optical properties with potential applications in medicinal chemistry and materials science.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Organic
Anissa Beghennou, Geoffrey Gontard, Heloise Dossmann, Kevin Passador, Serge Thorimbert, Vincent Corce, Candice Botuha
Summary: Efficient synthesis of original 1,6-naphthyridin-7(6H)-ones and their optical properties, including dual fluorescence, solvatochromism, acidochromism, large Stokes shifts, and high quantum yields, are described in this study. These properties make them suitable for biological applications or as luminescent devices in materials science.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Robin Ramos, Jeremy M. Zimbron, Serge Thorimbert, Lise-Marie Chamoreau, Annie Munier, Candice Botuha, Anthi Karaiskou, Michele Salmain, Joelle Sobczak-Thepot
DALTON TRANSACTIONS
(2020)
Article
Chemistry, Inorganic & Nuclear
Benjamin Doistau, Lorien Benda, Jean-Louis Cantin, Olivier Cador, Fabrice Pointillart, Wolfgang Wernsdorfer, Lise-Marie Chamoreau, Valerie Marvaud, Bernold Hasenknopf, Guillaume Vives
DALTON TRANSACTIONS
(2020)
Article
Chemistry, Multidisciplinary
Lorien Benda, Benjamin Doistau, Caroline Rossi-Gendron, Lise-Marie Chamoreau, Bernold Hasenknopf, Guillaume Vives
COMMUNICATIONS CHEMISTRY
(2019)
Article
Chemistry, Organic
Liang Chang, Serge Thorimbert, Luc Dechoux
ORGANIC & BIOMOLECULAR CHEMISTRY
(2019)
Review
Chemistry, Inorganic & Nuclear
Benjamin Doistau, Lorien Benda, Bernold Hasenknopf, Valerie Marvaud, Guillaume Vives