☆ 4.8 Article

A Trigonal Prismatic Mononuclear Cobalt(II) Complex Showing Single-Molecule Magnet Behavior

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015)

Get Full Text
Add to Collection

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 31, Pages 9792-9795

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b05739

Keywords

-

Categories

Chemistry, Multidisciplinary

Funding

  1. Russian Science Foundation [14-13-00724]
  2. EPSRC(UK) [EP/L018470/1]
  3. Engineering and Physical Sciences Research Council [EP/L018470/1] Funding Source: researchfish
  4. EPSRC [EP/L018470/1] Funding Source: UKRI
  5. Russian Science Foundation [14-13-00724] Funding Source: Russian Science Foundation

Ask authors/readers for more resources

Protocol

Community support

Reagent

Community support

Single-molecule magnets (SMMs) with one transition-metal ion often rely on unusual geometry as a source of magnetically anisotropic ground state. Here we report a cobalt(II) cage complex with a trigonal prism geometry showing single ion magnet behavior with very high Orbach relaxation barrier of 152 cm(-1). This, to our knowledge, is the largest reported relaxation barrier for a cobalt-based mononuclear SMM. The trigonal prismatic coordination provided by the macrocyclic ligand gives intrinsically more stable molecular species than previously reported SMMs, thus making this type of cage complexes more amendable to possible functionalization that will boost their magnetic anisotropy even further.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.8
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

Article Chemistry, Inorganic & Nuclear

Synthesis, crystal polymorphism and spin crossover behavior of adamantylboron-capped cobalt(ii) hexachloroclathrochelate and its transformation into the CoIIICoIICoIII-bis-macrobicyclic derivative

Alexander S. Belov, Valentin V. Novikov, Anna V. Vologzhanina, Alexander A. Pavlov, Artem S. Bogomyakov, Yan V. Zubavichus, Roman D. Svetogorov, Genrikh E. Zelinskii, Yan Z. Voloshin

Summary: This study investigates the fast crystallization and structural transformation of a cobalt (II) complex. The complex undergoes a temperature-induced spin crossover and its behavior is influenced by solvent and crystal polymorphism. The findings provide insights into the synthesis and properties of cobalt complexes.

DALTON TRANSACTIONS (2023)

Add to Collection
Article Biochemistry & Molecular Biology

Parahydrogen-Induced Hyperpolarization of Unsaturated Phosphoric Acid Derivatives

Veronika V. V. Zlobina, Alexey S. S. Kiryutin, Igor A. A. Nikovskiy, Oleg I. I. Artyushin, Vitaly P. P. Kozinenko, Alexander S. S. Peregudov, Alexandra V. V. Yurkovskaya, Valentin V. V. Novikov

Summary: Parahydrogen-induced nuclear polarization significantly enhances the sensitivity of NMR spectroscopy for medical diagnostics and enables the creation of new probes for magnetic resonance imaging. In this study, unsaturated derivatives of phosphoric acid, propargyl, and allyl phosphates, are proposed as precursors for biocompatible hyperpolarized probes. The polarization transfer to H-1 and P-31 nuclei of their hydrogenation products using ALTADENA, PASADENA, and the PH-ECHO-INEPT+ pulse sequence of NMR spectroscopy resulted in a highly amplified signal, which is among the largest for parahydrogen-induced nuclear polarization transfer to the P-31 nucleus.

INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES (2023)

Add to Collection
Article Biochemistry & Molecular Biology

Pyrrolidine-Derived Phenanthroline Diamides: An Influence of Fluorine Atoms on the Coordination of Lu(III) and Some Other f-Elements and Their Solvent Extraction

Nane A. Avagyan, Pavel S. Lemport, Mariia V. Evsiunina, Petr I. Matveev, Svetlana A. Aksenova, Yulia V. Nelyubina, Alexandr V. Yatsenko, Viktor A. Tafeenko, Vladimir G. Petrov, Yuri A. Ustynyuk, Xihe Bi, Valentine G. Nenajdenko

Summary: Three pyrrolidine-derived phenanthroline diamides were studied as ligands for lutetium trinitrate. The presence of halogen atoms in the structure of phenanthroline ligands has a significant impact on the coordination number of lutetium and the number of solvate water molecules. Fluorinated ligands showed higher efficiency based on the measured stability constants. Complexation with lutetium led to a shift in the F-19 NMR signal. The advantages of chlorinated and fluorinated pyrrolidine diamides in liquid-liquid extraction were demonstrated.

INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES (2023)

Add to Collection
Article Biochemistry & Molecular Biology

Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers

Igor A. Nikovskiy, Pavel V. Dorovatovskii, Valentin V. Novikov, Yulia V. Nelyubina

Summary: Two coordination polymers were obtained through a PCET-assisted process using the hydroxy-pyrazolyl moiety of the ligand and the iron(II) ion as sources of proton and electron. Under mild conditions, the first coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines was synthesized. Under harsh solvothermal conditions, a hydrogen atom transfer resulted in the transformation of hydroxyl groups, producing the third coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines. This PCET-assisted approach can be used to produce coordination polymers and metal-organic frameworks with the SCO-active core N-3(L)MN3(L).

MOLECULES (2023)

Add to Collection
Article Chemistry, Physical

Effect of Alkoxy Substituents on the Regioselectivity of Catalytic C-H Activation in Benzoic Acids: Experimental and DFT Study

Vladimir B. Kharitonov, Dmitry V. Muratov, Yulia V. Nelyubina, Dmitry A. Loginov

Summary: This study demonstrated the influence of catalyst and alkyne nature on the regioselectivity of rhodium-catalyzed annulation of alkoxy-substituted benzoic acids. X-ray diffraction and DFT calculation data showed that the regioselectivity was determined by both steric and coordination effects of methoxy groups. The findings are believed to be applicable to other C-H activation reactions of methoxy-substituted arene compounds.

CATALYSTS (2023)

Add to Collection
Article Chemistry, Multidisciplinary

3D-Shaped Binders of Unfolded Proteins Inducing Cancer Cell-Specific Endoplasmic Reticulum Stress In Vitro and In Vivo

Insa Klemt, Oleg Varzatskii, Roman Selin, Serhii Vakarov, Vladyslava Kovalska, Galyna Bila, Rostyslav Bilyy, Yan Voloshin, Itziar Cossio Cuartero, Andres Hidalgo, Benjamin Frey, Ina Becker, Bernhard Friedrich, Rainer Tietze, Ralf P. Friedrich, Christoph Alexiou, Elena-Laura Ursu, Alexandru Rotaru, Iris Solymosi, M. Eugenia Perez-Ojeda, Andriy Mokhir

Summary: The drug FeC 2 induces endoplasmic reticulum stress and increases ROS levels in cancer cells without affecting normal cells. It exhibits low micromolar toxicity towards various cancer cells and shows potential in suppressing primary tumor growth and metastases in murine models.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

Add to Collection
Article Chemistry, Physical

57Fe Mossbauer and DFT study of the electronic and spatial structures of the iron(ii) (pseudo)clathrochelates: the effect of ligand field strength

Denis V. V. Balatskiy, Alexander S. S. Chuprin, Semyon V. V. Dudkin, Luis Felipe Desdin-Garcia, Angel Luis Corcho-Valdes, Manuel Antuch, Vyacheslav M. M. Buznik, Svetlana Yu. Bratskaya, Yan Z. Z. Voloshin

Summary: A combined experimental and theoretical study was conducted on a series of iron(ii)-centered (pseudo)macrobicyclic analogs and homologs. The strength of the (pseudo)encapsulating ligand was found to influence the spin state of the iron(ii) ion and the electron density at its nucleus. The correlation between the isomer shift (IS) values and the electron density was successfully predicted using quantum-chemical calculations. However, the prediction of quadrupole splitting (QS) values based on theoretical calculations was challenging and could not be solved at the moment.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2023)

Add to Collection
Article Chemistry, Inorganic & Nuclear

Multistep synthesis and X-ray structures of carboxyl-terminated hybrid iron(II) phthalocyaninatoclathrochelates and their postsynthetic transformation into polytopic carboranyl-containing derivatives

Alexander S. Chuprin, Alexander A. Pavlov, Anna V. Vologzhanina, Pavel V. Dorovatovskii, Anton V. Makarenkov, Valentina A. Ol'shevskaya, Semyon V. Dudkin, Yan Z. Voloshin

Summary: A multistep synthetic strategy for polytopic carboranyl-containing (semi)clathrochelate metal complexes involving template synthesis, transmetallation, amide condensation, and 1,3-dipolar cycloaddition reactions is developed. Various precursors were obtained through transmetallation and macrobicyclization, and further condensation reactions led to the formation of carboranosemiclathrochelates and phthalocyaninatoclathrochelates. The resulting complexes were characterized by various techniques and exhibited interesting coordination geometries.

DALTON TRANSACTIONS (2023)

Add to Collection
Article Chemistry, Inorganic & Nuclear

Synthesis, X-ray structure and magnetic properties of the apically functionalized monocapped cobalt(ii) tris-pyridineoximates possessing SMM behaviour

Alexander S. S. Belov, Svetlana A. A. Belova, Nikolay N. N. Efimov, Veronika V. V. Zlobina, Valentin V. V. Novikov, Yulya V. V. Nelyubina, Yan V. V. Zubavichus, Yan Z. Z. Voloshin, Alexander A. A. Pavlov

Summary: Title: Cobalt(II) pseudoclathrochelate complexes exhibit an intermediate trigonal prismatic-trigonal antiprismatic geometry. According to PPMS data, they show SMM behavior with Orbach relaxation barriers of approximately 90 K. Paramagnetic NMR experiments confirm the persistence of these magnetic characteristics in solution. Therefore, targeted delivery of this 3D molecular platform to a specific biosystem can be accomplished through straightforward apical functionalization without significant changes.

DALTON TRANSACTIONS (2023)

Add to Collection
Article Chemistry, Physical

Precise Fingerprint Determination of Vibrational Infrared Spectra in a Series of Co(II) Clathrochelates through Experimental and Theoretical Analyses

Angel Luis Corcho-Valdes, Josue Ponce de Leon-Cabrera, Ivan Padron-Ramirez, Frank Justo Chao-Mujica, Ekaterina Lebed, Alejandro Gutierrez-Quintanilla, Luis Felipe Desdin-Garcia, Yan Voloshin, Manuel Antuch

Summary: The high demand for clean energy vectors in modern society has led to an increase in research on homogeneous and immobilized electrocatalysts that can replace Pt. Clathrochelates have shown promising electrocatalytic properties for the hydrogen evolution reaction (HER), but the exact mechanism of their catalysis is still under debate. This study aimed to determine the IR pattern and appropriate calculation methodology for a family of Co-(II) clathrochelates through theoretical and experimental analysis. The research provided valuable insights into the vibrational spectra and assignment of cobalt-(II) clathrochelates, which have complex spectra.

JOURNAL OF PHYSICAL CHEMISTRY A (2023)

Add to Collection
No Data Available
Webinars Posters Questions Hubs Funding Journals Papers Connect Collections Reviewers About Us FAQs Mobile App Privacy Policy Terms of Use
© Peeref 2019-2024. All rights reserved.