Review
Biochemistry & Molecular Biology
Dawit Tesfaye, Wolfgang Linert, Mamo Gebrezgiabher, Yosef Bayeh, Fikre Elemo, Taju Sani, Nandakumar Kalarikkal, Madhu Thomas
Summary: Supramolecular architectures formed by combining inorganic metal cations and organic ligands through self-assembly are a technique in modern chemical science. These multi-nuclear systems have various applications including sensing, storage/cargo, display, and molecular switching. Iron(II) mediated spin-crossover (SCO) supramolecular architectures with Schiff base ligands have gained attention due to their unique structures and potential applications. This review article discusses the various geometrical possibilities and the structural and SCO behavior of these complexes.
Article
Materials Science, Multidisciplinary
N. Kazak, M. S. Platunov, Yu Knyazev, M. S. Molokeev, M. Gorev, S. G. Ovchinnikov, Z. Pchelkina, V. V. Gapontsev, S. Streltsov, J. Bartolome, A. Arauzo, V. V. Yumashev, S. Yu Gavrilkin, F. Wilhelm, A. Rogalev
Summary: In this study, the spin and oxidation states of Co in Co3BO5 were investigated using XMCD and magnetic susceptibility measurements. Results show that at low temperatures, Co2+ ions are in the HS state while Co3+ ions are in the LS state. The crystal structure shows anomalies at high temperatures.
Article
Chemistry, Physical
Thilini K. Ekanayaka, Hannah Kurz, Kayleigh A. McElveen, Guanhua Hao, Esha Mishra, Alpha T. N'Diaye, Rebecca Y. Lai, Birgit Weber, Peter A. Dowben
Summary: The spin state transition behavior of Fe(ii) spin crossover coordination polymer crystallites at the surface differs from the bulk, possibly due to factors such as oxidation, differences in surface packing, and changes in coordination. Some Fe(ii) spin crossover coordination polymers may be photoactive enough to prevent discernment of the spin state transition using X-ray spectroscopies.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Review
Chemistry, Inorganic & Nuclear
Bijoy Dey, Vadapalli Chandrasekhar
Summary: This review focuses on spin crossover phenomena, particularly in Fe-II complexes in the N4O2 coordination environment. It discusses three ligand families: Jager-type ligands, hydrazone-based ligands, and tridentate ligands with salicylaldehyde derivatives. It explores the assembly of mononuclear and multinuclear complexes, as well as the coupling of optical and magnetic properties.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Veronica Jornet-Molla, Carlos Gimenez-Saiz, Dmitry S. Yufit, Judith A. K. Howard, Francisco M. Romero
Summary: The spin crossover salt [Fe(bpp)(2)](isonicNO)(2). 2.4 H2O undergoes a very abrupt spin crossover at 274.4 K, with reversible response to light irradiation or temperature change; Isotopic effects in the thermomagnetic behavior highlight the significance of hydrogen bonds in determining the magnetic state; The compound can be reversibly dehydrated to produce 1, which also exhibits spin crossover coupled with H-bond isomerization, resulting in strong kinetic effects in the thermomagnetic properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Blake J. P. Connolly, Victor Brosius, Nicole Mertes, Caroline Demidova, Jessica K. Bilyj, Mark J. Riley, Paul Bernhardt
Summary: A series of isostructural rhombohedral salts [Fe(tame)(2)]X-2.MeOH were studied for their temperature dependent structures and spin crossover behavior. The [Fe(tame)(2)]Br-2.MeOH compound exhibited spin crossover at very low temperatures, while [Fe(tame)(2)]X-2.nMeOH (X=ClO4- and BF4-) compounds remained in their high spin form. Removal of the MeOH solvent from [Fe(tame)(2)]X-2.MeOH compounds led to reversible loss of crystallinity, with the fluoride and trifluoromethanesulfonate salts of [Fe(tame)(2)](2+) showing no spin crossover behavior.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Physics, Condensed Matter
Saliou Bolarinwa Ogou, Toussaint Djidjoho Oke, Mounirou Karimou, Felix Hontinfinde, Kamel Boukheddaden
Summary: We have investigated the magnetic phase diagrams of spin-crossover (SCO) solids using the Blume-Emery-Griffiths spin-1 model. Our findings show thermally-induced gradual and first-order spin-transitions by varying the model parameters. Various types of isothermal magnetic hysteresis loops are obtained near the first-order transition, and their coercive fields and loop patterns are discussed as a function of temperature.
JOURNAL OF PHYSICS-CONDENSED MATTER
(2023)
Article
Chemistry, Physical
Shiladitya Karmakar, Pradip Chakraborty, Tanusri Saha-Dasgupta
Summary: In this computational study, the light-induced excited spin-state trapping (LIESST) in Fe(ii) spin crossover complexes coordinated by different types of ligands was investigated to elucidate the trend in the low temperature relaxation rate. The results show a nine order of magnitude change in the relaxation rate among the complexes. This trend can be rationalized by considering the change in metal-ligand covalency, which affects the back donation or delocalization of the electrons from the low-lying Fe(ii)-centered molecular orbital to the empty low-lying ligand-centered pi* antibonding molecular orbitals.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Inorganic & Nuclear
Narsimhulu Pittala, Emmelyne Cuza, Dawid Pinkowicz, Michal Magott, Mathieu Marchivie, Kamel Boukheddaden, Smail Triki
Summary: A new 1D coordination polymer has been synthesized and characterized. The magnetic and vibrational infrared data analysis reveals the contribution of two Fe-II active centers. Photomagnetic experiment shows that the dehydrated phase exhibits a photomagnetic response.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Maria Jose Heras Ojea, Jeff M. Van Raden, Shayan Louie, Richard Collins, Daniel Pividori, Jordi Cirera, Karsten Meyer, Ramesh Jasti, Richard A. Layfield
Summary: The addition of bipyridyl-embedded cycloparaphenylene nanohoop to an iron(II) complex leads to a distorted octahedral structure with spin-crossover behavior. Computational studies suggest that the size and curvature of the nanohoop play a critical role in determining the SCO properties of the iron(II) complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Shufang Xue, Yunnan Guo, Yann Garcia
Summary: Spin crossover technology continues to attract worldwide attention, with many potential applications envisioned, but there are still challenges in achieving spin state switching between discrete molecular crystals in crystal materials.
Article
Chemistry, Inorganic & Nuclear
Sipeng Zheng, Silvia Spa, Erik P. van Geest, Jan M. van Ruitenbeek, Sylvestre Bonnet
Summary: This study describes the synthesis of a new tetrapyridyl ligand and its iron(II) complex, as well as the investigation of their self-assembly on surfaces. The results suggest that these molecules can self-assemble into highly ordered monolayers, providing important insights for the development of spin-switching materials.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Francesca Milocco, Folkert de Vries, Harmke S. Siebe, Silene Engbers, Serhiy Demeshko, Franc Meyer, Edwin Otten
Summary: This study investigated how steric effects, pi-stacking interactions, and electronic substituent effects impact the spin-crossover behavior of Bis(formazanate)iron(II) complexes. Six new compounds were synthesized and characterized, with the inclusion of additional OMe donors resulting in a significant shift in spin-crossover temperatures.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Weiyang Li, Cuilian Liu, Joseph Kfoury, Julianna Olah, Koen Robeyns, Michael L. Singleton, Serhiy Demeshko, Franc Meyer, Yann Garcia
Summary: A Fe-II based supramolecular cage with pyridyl-hydrazone ligand scaffolds displaying temperature induced spin crossover behavior was reported, and density functional theory calculations were used to investigate the cause of this phenomenon based on the ligand structure. The results suggest that low-spin cages with pyridyl-imine sites could potentially undergo spin crossover when carefully manipulating the functional groups in the ligand system.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Lee T. Birchall, Amber T. Raja, Lewis Jackson, Helena J. Shepherd
Summary: To improve strategies for spin-crossover material design, obtaining isostructural materials is crucial for developing and understanding structure-property relationships. In this study, we synthesized four isostructural cocrystal solvates using a specific complex and coformer. The spin-crossover properties of these materials were determined by single-crystal X-ray diffraction and were found to be influenced by the hydrogen bond basicity of the anions and solvents present.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Jana Jurakova, Jana Dubnicka Midlikova, Jakub Hruby, Andrii Kliuikov, Vinicius Tadeu Santana, Jan Pavlik, Jan Moncol', Erik Cizmar, Milan Orlita, Ivan Mohelsky, Petr Neugebauer, Denis Gentili, Massimiliano Cavallini, Ivan Salitros
Summary: Four pentacoordinate complexes have been synthesized and their structures determined. The magnetic properties of the compounds were investigated, and the relationship between geometry and orbital ordering was discussed. Theoretical calculations were in good agreement with experimental data. Wet lithographic technique was used to evaluate the processability of the complexes and the preparation of microstructured films.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Materials Science, Multidisciplinary
Xuan Thang Cao, Subodh Kumar, Ivan Nemec, Josef Kopp, Rajender S. Varma
Summary: Bi-functional covalent organic polymers with distinctive morphologies were synthesized by solvent switching. The synthesized polymers showed similar chemical properties and their catalytic activity was morphology-dependent.
FRONTIERS IN MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Karin Preinerova, Miroslava Puchonova, Martin Schoeller, Vladimir Kuchtanin, Noemi Molnarova, Svetlana Krystofova, Milan Mazur, Ivan Il'ko, Viera Peterkova, Jan Moncol
Summary: Three new methylsalicylatocopper and four methylbenzoatocopper complexes were synthesized and characterized. The complexes exhibited antimicrobial and antifungal activities, as well as acaricidal activity against Phytoseiulus perimilis.
Article
Chemistry, Inorganic & Nuclear
Martin Schoeller, Karin Preinerova, Vladimir Jorik, Milan Mazur, Jan Moncol'
Summary: A new mononuclear manganese(II) complex with a chlorido-substituted hexadentate Schiff base ligand was synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The complex exhibited a triclinic crystal system with a P1 space group. The manganese(II) central atom was coordinated by two oxygen atoms and four nitrogen atoms of the Schiff base. The supramolecular structure and intermolecular interactions of the complex were analyzed using Hirshfeld surface analysis. Characterization of the complex was done using UV-vis and infrared spectra, and the presence of a high-spin Mn(II) state (S = 5/2) was confirmed by solid-state EPR spectroscopy.
INORGANIC CHEMISTRY COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ivana Loubalova, Eva Zahradnikova, Lukas Masaryk, Ivan Nemec, Lucie Hochvaldova, Ales Panacek, Libor Kvitek, Renata Vecerova, Marcin Swiatkowski, Pavel Kopel
Summary: A series of nickel and copper complexes were synthesized and characterized. These complexes exhibited moderate antibacterial activity and could potentially be used to treat skin wounds.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Jakub Orvos, Robert Fischer, Barbora Brachnakova, Jan Pavlik, Jan Moncol, Alexandra Sagatova, Marek Fronc, Jozef Kozisek, Lucie Routaboul, Azzedine Bousseksou, Ivan Salitros
Summary: A series of phenylazo-substituted derivatives of pyridyl-benzimidazoles L1-L5 were synthesized via a modified Mills reaction and their structural, spectral and photoswitching properties were investigated. NMR spectroscopy and single-crystal X-ray diffraction analysis confirmed the E conformation of the desired compounds. UV-VIS and H-1 NMR spectroscopy revealed reversible photochromic behavior of the compounds, and computational studies helped explain the conversion and mechanisms of photoisomerization. In addition, four ferrous coordination compounds C1-C4 were prepared using ligands L1 and L2, and their structural and magnetic properties were studied.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nikoleta Malinova, Jana Jurakova, Barbora Brachnakova, Jana Dubnicka Midlikova, Erik Cizmar, Vinicius Tadeu Santana, Radovan Herchel, Milan Orlita, Ivan Mohelsky, Jan Moncol, Petr Neugebauer, Ivan Salitros
Summary: The synthesis of a mononuclear Co(II) complex 1 using a novel tridentate ligand L was investigated. The molecular structure of complex 1 was confirmed by single-crystal X-ray structural analysis and noncovalent contacts were examined. The magnetic properties of complex 1 were analyzed using the Griffith-Figgis Hamiltonian, and calculations and spectroscopic study showed good agreement. The AC magnetic investigation revealed slow relaxation of magnetization in complex 1 with involvement of direct, Raman, and Orbach processes.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Biochemistry & Molecular Biology
Jan Gettler, Tomas Carny, Martin Markovic, Peter Koos, Erika Samol'ova, Jan Moncol', Tibor Gracza
Summary: A versatile strategy for the enantioselective synthesis of a benzo[c]oxepine structural core containing natural secondary metabolites was developed. The key steps of the synthetic approach include ring-closing alkene metathesis, Suzuki-Miyaura cross-coupling reaction, and Katsuki-Sharpless asymmetric epoxidation. The total synthesis and absolute configuration assignment of heterocornol D were achieved, and the synthesis of heterocornol C was presented as an extension of the described approach.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Martin Schoeller, Milan Piros, Miroslava Litecka, Katarina Konarikova, Flora Jozefikova, Alexandra Sagatova, Eva Zahradnikova, Jindra Valentova, Jan Moncol
Summary: This article presents eight novel octahedral ruthenium(II) complexes with 2,2'-bipyridine molecules and salicylates as ligands, differing in the position and type of halogen substituent. The complexes were characterized by X-ray structural analysis and NMR spectroscopy, as well as spectral methods such as FTIR, UV-Vis, and ESI-MS. The complexes showed sufficient stability in solutions and were studied for their biological properties, including binding ability to BSA, interaction with DNA, and in vitro antiproliferative effects against MCF-7 and U-118MG cell lines. Some of the complexes exhibited anticancer effects against these cell lines.
Article
Polymer Science
Maximilian Seydi Kilic, Jules Brehme, Justus Pawlak, Kevin Tran, Friedrich Wilhelm Bauer, Takuya Shiga, Taisei Suzuki, Masayuki Nihei, Ralf Franz Sindelar, Franz Renz
Summary: We synthesized iron(II)-triazole spin crossover compounds and incorporated them into electrospun polymer nanofibers. The polymer complex composites with intact switching properties were obtained using two separate electrospinning methods. The analysis of the complexes and composites showed that the spin crossover properties were maintained after the electrospinning processes.
Article
Chemistry, Inorganic & Nuclear
Milan Piros, Martin Schoeller, Katarina Konarikova, Jindra Valentova, Lubomir Svorc, Jan Moncol, Marian Valko, Jozef Svorec
Summary: In this study, five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates were synthesized and characterized. The complexes exhibited antioxidant and anticancer activities, and interacted with DNA and serum albumin. Among them, complex 4 showed moderate anticancer activity against MCF-7 cancer cells.
Article
Chemistry, Inorganic & Nuclear
Radka Krikavova, Michaela Romanovova, Zuzana Jendzelovska, Martin Majernik, Lukas Masaryk, Pavel Zoufaly, David Milde, Jan Moncol, Radovan Herchel, Rastislav Jendzelovsky, Ivan Nemec
Summary: Half-sandwich complexes with thiadiazole-based ligand showed hydrolytic stability, catalytic activity, and selective inhibitory effects on cancer cells.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Romana Micova, Cyril Rajnak, Jan Titis, Alina Bienko, Jan Moncol, Erika Samolova, Roman Boca
Summary: Two hexacoordinate Co(II) complexes were synthesized and characterized. Their unique elongated tetragonal bipyramid geometry required the use of the Griffith-Figgis model to analyze the magnetic data. The ground electronic term of these complexes was quasi-degenerate due to crystal field splitting, resulting in four Kramers doublets that exhibited a significant mixing of spins. Both complexes showed field-supported slow magnetic relaxation governed by the Raman process.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Lukas Masaryk, Denisa Weiser Drozdkova, Karolina Sloczynska, Jan Moncol, David Milde, Radka Krikavova, Justyna Popiol, Elzbieta Pekala, Katarina Ondruskova, Ivan Nemec, Katerina Smesny Trtkova, Pavel Starha
Summary: This study presents easy-to-prepare diiodidoplatinum(II) complexes that show significant anticancer effects against multiple myeloma cells with low toxicity to normal cells. The complexes are more effective against myeloma cells and induce apoptosis through a different mechanism compared to cisplatin. These findings suggest that the non-classical platinum(II) complexes have potential as a monotherapy for hard-to-treat multiple myeloma.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Andre Niebur, Aljoscha Soell, Philipp Haizmann, Onno Strolka, Dominik Rudolph, Kevin Tran, Franz Renz, Andre Philipp Frauendorf, Jens Huebner, Heiko Peisert, Marcus Scheele, Jannika Lauth
Summary: 2D semiconducting transition metal dichalcogenides (TMDCs) show an ultrafast response to optical stimuli, making them highly promising for future optoelectronic applications. Colloidal nanochemistry is an emerging synthesis method for controlling the reaction and producing 2D TMDC nanosheets with small lateral sizes. In this study, the synthesis of 2D mono- and bilayer MoS2 nanoplatelets and MoS2 nanosheets was achieved by adjusting the molybdenum precursor concentration. The resulting MoS2 nanosheets underwent a transformation to the semiconducting crystal phase, showing potential for future colloidal photonics applications.
