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, Inorganic & Nuclear
Qianqian Yang, Yin-Shan Meng, Tao Liu, Jinkui Tang
Summary: The study of two iron(o) complexes reveals that the spin states and spin-crossover behavior are influenced by supramolecular interactions and crystal packing effects. Complex 1·ClO4 shows light-induced excited spin state trapping and two-step spin-crossover at room temperature, while complex 1·BF4 exhibits gradual spin-crossover behavior. Magnetostructural analysis provides insight into the differences in the spin-crossover properties of the two complexes.
DALTON TRANSACTIONS
(2022)
Review
Chemistry, Inorganic & Nuclear
Olesia Kucheriv, Igor O. Fritsky, Il'ya A. Gural'skiy
Summary: SCO compounds are a large class of switchable coordination complexes that can change their electronic configurations under different external stimuli, showing potential applications in various fields. Cyanometallic frameworks exhibit SCO properties, providing insights into new materials with desired spin-crossover characteristics, with the reduction to nanometre scale impacting their performance.
INORGANICA CHIMICA ACTA
(2021)
Article
Chemistry, Multidisciplinary
Liang Zhao, Yin-Shan Meng, Qiang Liu, Osamu Sato, Quan Shi, Hiroki Oshio, Tao Liu
Summary: The study reports a magnetic bistable material consisting of specific compounds that can undergo multiple magnetic states transitions induced by light, showing behaviors of single-chain magnets and single-molecule magnets.
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, Inorganic & Nuclear
Hai-Lang Zhu, Yan-Rui Lei, Yin-Shan Meng, Tao Liu, Hiroki Oshio
Summary: In this study, a two-dimensional spin crossover complex was successfully synthesized by incorporating the bridging ligand 4,4'-Bis-(1H-imidazol1-yl-methyl)biphenyl (bimb) into a cyanide-bridged FeII-MoV assembly. The complex exhibited an incomplete spin transition with approximately 62% of the high-spin (HS) FeII species transitioning to the low-spin (LS) FeII state upon cooling.
INORGANIC CHEMISTRY COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Shintaro Kawabata, Koji Nakabayashi, Kenta Imoto, Stephen Klimke, Franz Renz, Shin-ichi Ohkoshi
Summary: By incorporating chiral organic ligands into cyanido-bridged Fe-II-Nb-IV assemblies, chiral spin-crossover complexes with non-centrosymmetric structure and second harmonic generation capability were successfully synthesized. All complexes exhibit spin crossover between high-spin and low-spin Fe-II states without thermal hysteresis. Chiral complexes of R-FeNb and S-FeNb demonstrate second harmonic generation due to their non-centrosymmetric structure.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Evridiki Michaels, Izar Capel Berdiell, Hari Babu Vasili, Christopher M. Pask, Mark J. Howard, Oscar Cespedes, Malcolm A. Halcrow
Summary: The complex salts [FeL2]X2 exhibit spin-transitions at specific temperatures, with a significant effect of thermally induced excited spin-state trapping observed in 1[ClO4]2. The crystal structure of 1[BF4]2 undergoes a phase transition at different temperatures, while the phase transition in 1[ClO4]2 remains unchanged between 100 and 300 K.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Physics, Applied
Shintaro Kawabata, Koji Nakabayashi, Kenta Imoto, Shin-ichi Ohkoshi
Summary: A spin crossover material based on a cyanido-bridged Fe-II-Mo-IV assembly exhibits incomplete spin crossover with a unique molecular arrangement due to elastic frustration between high-spin and low-spin Fe-II sites. Thermal hysteresis is not observed in this compound with a cubic crystal structure.
JOURNAL OF APPLIED PHYSICS
(2021)
Article
Chemistry, Physical
Marc Alias-Rodriguez, Swarnendu Bhattacharyya, Miquel Huix-Rotllant
Summary: Photoexcitation of [Fe-II(2,2'-bipyridine)(3)](2+) causes a subpicosecond spin crossover transformation from a low-spin singlet to a high-spin quintet state. Through quantum wavepacket dynamics, it is shown that metal-centered triplets play a catalytic role in the transition to the high-spin state. By breaking conjugation, the lifetime of MLCT states can be increased, thereby increasing the energy gap between MLCT and MC states.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Review
Chemistry, Inorganic & Nuclear
Manabu Nakaya, Ryo Ohtani, Leonard F. Lindoy, Shinya Hayami
Summary: This review provides an overview of reported examples of SCO iron(III) systems that exhibit the LIESST effect, which is crucial for understanding the excited states and spin state transitions in iron(III) complexes.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Physics, Applied
J. Cruddas, G. Ruzzi, B. J. Powell
Summary: A simple two-dimensional model of spin crossover materials leads to the emergence of spin-state smectic phases, which exhibit unique characteristics in terms of breaking rotational symmetry and translational symmetry in one direction only. These smectic phases result in plateaus in the fraction of high-spin metal centers and lines of Bragg peaks in x-ray and neutron scattering structure factors. The ordering of the smectic phases is unidirectional, with residual entropy scaling with the linear dimension of the system, contrasting with spin-state ices and antiferroelastic ordered phases.
JOURNAL OF APPLIED PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Nicolas Montenegro-Pohlhammer, Rocio Sanchez-de-Armas, Carmen J. Calzado
Summary: The study investigates the molecular level interaction of the spin-crossover (SCO) Fe-II((3,5-(CH3)(2)Pz)(3)BH)(2) complex with the Au(111) surface, revealing that adsorption on the metallic surface enhances transition energy and increases the relative stability of the low spin state, with a spin-dependent interaction stronger for low spin than high spin. The different strength of the Fe ligand field at low and high temperatures is reflected in the nature of states close to the Fermi level, with larger metal-ligand hybridization in the low spin state.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Jiajia Li, Xiao-Peng Sun, Shiqi Bi, Minglu Xu, Siyu Jia, Zheng Tang, Pengtao Ma, Jingping Wang, Jun Tao, Jingyang Niu
Summary: This study successfully integrated polyoxometalate (POM) anions into the Fe(II) spin crossover (SCO) system and found that POM anions play an effective role in regulating spin-state switching properties.
INORGANIC CHEMISTRY
(2022)
Article
Environmental Sciences
Jesus Gonzalez-Cobos, Barbara Rodriguez-Garcia, Mabel Torrens, Oscar Alonso-Almirall, Marti Aliaguilla, David Gali, David Gutierrez-Tauste, Magi Galindo-Anguera, Felipe A. Garces-Pineda, Jose Ramon Galan-Mascaros
Summary: Research on generating high-purity green hydrogen via seawater electrolysis is ongoing, showing potential but still facing challenges to meet industrial standards.
Article
Chemistry, Physical
Chang Quo, Alba Villar-Yanez, Diego Garay-Ruiz, Jordi-Benet Buchholz, Caries Bo, Arjan W. Kleij
Summary: Structurally diverse heterobicyclic diethers can be conveniently synthesized using a binary catalyst, which has potential applications in various fields. Mechanistic studies and computational investigations have provided insights into the reaction pathway and the role of the catalyst, laying a foundation for further research.
Article
Chemistry, Multidisciplinary
Bing Jiang, Marcos Gil-Sepulcre, Pablo Garrido-Barros, Carolina Gimbert-Surinach, Jia-Wei Wang, Jordi Garcia-Anton, Pau Nolis, Jordi Benet-Buchholz, Nuria Romero, Xavier Sala, Antoni Llobet
Summary: A cobalt complex with a kappa-N3P2 ligand is stable in air and exhibits good electrochemical behavior. It can catalyze the hydrogen evolution reaction and be regenerated with the addition of CoCp*(2).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Craig S. Day, Cuong Dat Do, Carlota Odena, Jordi Benet-Buchholz, Liang Xu, Cina Foroutan-Nejad, Kathrin H. Hopmann, Ruben Martin
Summary: In this study, we report the synthesis of highly reduced bipyridyl magnesium complexes and the first stable organic magnesium electride supported by quantum mechanical computations and X-ray diffraction. These complexes act as unconventional homogeneous reductants due to their high solubility, modular redox potentials, and formation of insoluble, non-coordinating byproducts. The applicability of these reductants is demonstrated by accessing low-valent (bipy)2Ni(0) species that are otherwise challenging to access.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Andrea Moneo-Corcuera, David Nieto-Castro, Jordi Cirera, Veronica Gomez, Jesus Sanjose-Orduna, Carla Casadevall, Gabor Molnar, Azzedine Bousseksou, Teodor Parella, JoseMaria Martinez-Agudo, Julio Lloret-Fillol, Monica Helvia Perez-Temprano, Eliseo Ruiz, Jose Ramon Galan-Mascaros
Summary: Bistable molecules have the potential to be the miniaturization limit for high-density information technologies. However, their memory effect is typically observed at very low temperatures. In this study, we report the discovery of a slow relaxation process in an SCO iron-triazole poly-anionic complex, breaking the previous fast spin-state interconversion. Experimental evidences confirm the presence of thermal hysteresis in solid dilution and liquid solution, while density functional theory calculations reveal the origin of this phenomenon. These findings demonstrate the possibility of storing information at room temperature using SCO molecules, opening new opportunities for molecular data storage.
Article
Chemistry, Inorganic & Nuclear
Alvaro Seijas-Da Silva, Jose Alberto Carrasco, Bruno J. C. Vieira, Joao C. Waerenborgh, Eugenio Coronado, Gonzalo Abellan
Summary: In this study, a hybrid NiFe-LDH family is synthesized through anion exchange reactions using surfactant molecules, increasing the interlayer space and achieving complete magnetic decoupling of the layers. The results of magnetic analysis and Mossbauer spectroscopy validate the potential of molecular engineering for designing hybrid layered magnetic materials approaching the 2D magnetic limit.
DALTON TRANSACTIONS
(2023)
Article
Biochemistry & Molecular Biology
Joao P. L. Guerra, Clement E. Blanchet, Bruno J. C. Vieira, Joao C. Waerenborgh, Nykola C. Jones, Soren Vronning Hoffmann, Alice S. Pereira, Pedro Tavares
Summary: DNA-binding proteins from starved cells (Dps) are small multifunctional nanocages expressed by prokaryotes as a bacterial defense mechanism. They protect bacterial DNA from damage by binding directly or removing precursors of reactive oxygen species. The conformation of the N-terminal tails of Dps proteins is altered upon metal binding in a reversible and specific manner, indicating a potential regulatory process for their DNA-binding properties through metal binding to their N- and/or C-terminal extensions.
Article
Chemistry, Multidisciplinary
Xuetong Li, Jordi Benet-Buchholz, Eduardo C. Escudero-Adan, Arjan W. Kleij
Summary: A conceptually novel catalytic domino approach is presented for the synthesis of highly functional 1,4-dihydro-2H-1,3-benzoxazine-2-one derivatives. The chemoselectivity is achieved through a proper design of the precursor and the use of Thorpe-Ingold effects. The synthetic diversity of these CO2-based heterocycles is demonstrated, and an unusual ring-expansion sequence is observed from an alpha-alkylidene, five-membered cyclic carbonate to a six-membered cyclic carbamate by N-induced isomerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Aleria Garcia-Roca, Raul Perez-Soto, Georgiana Stoica, Jordi Benet-Buchholz, Feliu Maseras, Arjan W. Kleij
Summary: Metal-catalyzed propargylic transformations are a powerful tool in organic synthesis for forming new carbon-carbon and carbon-heteroatom bonds. However, there is limited knowledge about the mechanistic intricacies of asymmetric propargylic reactions with challenging heteroatom substitution, presenting an inspiring challenge. This study presents a detailed mechanistic analysis of a propargylic sulfonylation reaction promoted by a chiral Cu catalyst through experimental techniques and computational studies. Surprisingly, the enantio-discriminating step was found to be the proto-demetalation step, rather than the coupling between the nucleophile and the propargylic precursor.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Qian Zeng, Fengyun Gao, Jordi Benet-Buchholz, Arjan W. Kleij
Summary: A modular and practical method has been developed for the synthesis of complex allylic alcohols through a three-component reaction using dual photoredox/Ni catalysis. This method allows for high regio- and stereoselectivity and provides access to compounds with sterically congested and functionalized quaternary carbon centers. The stereoselectivity can be reversed by changing the photocatalyst.
Article
Chemistry, Multidisciplinary
Mario Palacios-Corella, Victor Garcia-Lopez, Joao Carlos Waerenborgh, Bruno J. C. Vieira, Guillermo Minguez Espallargas, Miguel Clemente-Leon, Eugenio Coronado
Summary: A bifunctionalized polyoxometalate containing a redox active hexavanadate moiety and two tridentate 2,6-bis(pyrazol-1-yl)pyridine ligands was synthesized and characterized. Reaction with Fe(ii) or Zn(ii) ions resulted in the formation of crystalline 1D networks with tunable magnetic and redox properties. The structures exhibited spin-crossover behavior, which could be induced by light irradiation, and reversible solvent exchange. Additionally, the hexavanadate unit could be reduced and reoxidized, leading to changes in the spin state of Fe(ii) and creating a multifunctional material that can be controlled by various stimuli.
Article
Chemistry, Physical
Isabel Abanades Lazaro, Eleni C. Mazarakioti, Eduardo Andres-Garcia, Bruno J. C. Vieira, Joao C. Waerenborgh, Inigo J. Vitorica-Yrezabal, Monica Gimenez-Marques, Guillermo Minguez Espallargas
Summary: Two ultramicroporous 2D and 3D iron-based Metal-Organic Frameworks (MOFs) were synthesized through solvothermal synthesis, using different ratios and concentrations of precursors. These MOFs have reduced pore spaces decorated with pendant pyridine from tangling isonicotinic ligands, enabling them to achieve size-exclusion kinetic gas separation and thermodynamic separation, resulting in efficient and renewable CO2/N2 selectivity for dynamic breakthrough gas separation.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Enrique Burzuri, Maria Jose Martinez-Perez, Carlos Marti-Gastaldo, Marco Evangelisti, Samuel Manas-Valero, Eugenio Coronado, Jesus I. Martinez, Jose Ramon Galan-Mascaros, Fernando Luis
Summary: In this article, a novel 2D heterometallic oxalate complex is presented as a potential candidate for quantum spin liquid (QSL) material. It exhibits strong antiferromagnetic correlations and the absence of magnetic ordering, making it an appealing QSL candidate.
Article
Chemistry, Multidisciplinary
Claudio Ampelli, Daniele Giusi, Matteo Miceli, Tsvetelina Merdzhanova, Vladimir Smirnov, Ugochi Chime, Oleksandr Astakhov, Antonio Jose Martin, Florentine Louise Petronella Veenstra, Felipe Andres Garces Pineda, Jesus Gonzalez-Cobos, Miguel Garcia-Tecedor, Sixto Gimenez, Wolfram Jaegermann, Gabriele Centi, Javier Perez-Ramirez, Jose Ramon Galan-Mascaros, Siglinda Perathoner
Summary: A major challenge in energy transition is the development of efficient artificial leaf-type devices that can convert CO2, water, and sunlight into sustainable fuels and chemicals. We report top-level results in converting CO2 and H2O to fuels using sunlight and electrodes made of earth-abundant materials, without sacrificial donors or electrical bias. Our cell provides high solar-to-fuel efficiency and current densities, making it a promising solution for affordable artificial-leaf type systems in the future.
ENERGY & ENVIRONMENTAL SCIENCE
(2023)
