Review
Chemistry, Multidisciplinary
Esther Resines-Urien, Estefania Fernandez-Bartolome, Ana Martinez-Martinez, Arturo Gamonal, Lucia Pineiro-Lopez, Jose Sanchez Costa
Summary: Coordination complexes based on transition metal ions with [Ar]3d(4)-3d(7) electronic configurations can undergo a remarkable switchable phenomenon known as Spin Crossover (SCO). SCO is a detectable, reproducible, and reversible switch between the high spin (HS) and low spin (LS) electronic states of the transition metal, induced by various stimuli. This review presents a comprehensive compilation of iron coordination compounds that exhibit color change due to the interaction between the compounds and vapor analytes, coupled with a spin transition at room temperature.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Ryohei Akiyoshi, Yuki Komatsumaru, Masaki Donoshita, Shun Dekura, Yukihiro Yoshida, Hiroshi Kitagawa, Yasutaka Kitagawa, Leonard F. Lindoy, Shinya Hayami
Summary: The article investigates the ferroelectric spin crossover behavior in a cobalt(II) complex and finds that the flip-flop motion of the fluorophenyl ring can affect the spin state conversion. Confirmation of this effect is provided through single crystal X-ray structures, magnetic susceptibility measurements, and solid-state NMR spectroscopy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Multidisciplinary
Anna Vogel, Alfred Rabenbauer, Philipp Deng, Ruben Steib, Thorben Boeger, Wolfgang G. Zeier, Renee Siegel, Juergen Senker, Dominik Daisenberger, Katharina Nisi, Alexander W. Holleitner, Janio Venturini, Tom Nilges
Summary: A diode requires the combination of p- and n-type semiconductors or certain doping levels to function. However, the discovery of pnp-switchable compounds like Ag10Te4Br3 opens up the possibility of fabricating diodes from a single material. Ag18Cu3Te11Cl3, as a room temperature pnp-switching material, is the first single-material position-independent diode.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Shuting Liu, Zhenhua Zhu, Xiao-Lei Li, Jinkui Tang
Summary: A Fe(II) complex with long aliphatic chains and reversible switching property has been synthesized and characterized, demonstrating the mechanism of spin-crossover behavior and its association with a high-temperature phase transition through various experimental methods.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Multidisciplinary Sciences
Timur Ashirov, Julya Stein Siena, Mengru Zhang, A. Ozgur Yazaydin, Markus Antonietti, Ali Coskun
Summary: This study demonstrates light-switchable gas separation membranes based on polymeric carbon nitride with fast response times and efficient separation performance.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Kuppusamy Senthil Kumar, Mario Ruben
Summary: This review covers the advances in vacuum-sublimable SCO complexes, including the design and synthesis of functional SCO complexes, on-surface SCO of thin films, and various device architectures based on sublimable SCO complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sven Johannsen, Sascha Ossinger, Jan Grunwald, Alexander Herman, Heiko Wende, Felix Tuczek, Manuel Gruber, Richard Berndt
Summary: The Co-based complex deposited on Ag(111) was investigated. Due to a bis(tridentate) coordination sphere, the molecules formed tetramers. Individual complexes in these tetramers undergo reversible transitions between two states with characteristic image contrasts when current is passed through them or one of their neighbors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jinyoung Seo, Jason D. Braun, Vidhya M. Dev, Jarad A. Mason
Summary: Barocaloric effects, induced by applied hydrostatic pressure, offer promise for solid-state refrigerants. The pressure-induced spin-crossover transitions in a molecular iron(II) complex have been found to drive giant and reversible barocaloric effects, providing new insights for the design of barocaloric materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Pablo Roseiro, Nadia Ben Amor, Vincent Robert
Summary: The spin states of a Co(II) oxoverdazyl compound are investigated in this study. The results show a mixture of low-spin and high-spin states, which is influenced by the structure of the coordination sphere. This finding has significant implications for molecular magnetism.
Review
Chemistry, Inorganic & Nuclear
Mohammad Khurram Javed, Arshia Sulaiman, Masahiro Yamashita, Zhao-Yang Li
Summary: The spin crossover (SCO) phenomenon has made remarkable progress in applications, particularly in materials exhibiting SCO-luminescence synergy. This review aims to provide an overview of the luminescent and magnetic properties of SCO materials, synthesis strategies, and progress made in constructing such materials over the years.
COORDINATION CHEMISTRY REVIEWS
(2022)
Review
Chemistry, Multidisciplinary
Ramon Torres-Cavanillas, Miguel Gavara-Edo, Eugenio Coronado
Summary: The field of spin-crossover complexes is transitioning from studying the spin transition phenomenon to its application in molecular electronics. Processing spin-crossover materials as nanoparticles is a convenient way to maintain the bistability and reduce size. This paper reviews the recent advances in the chemical design of these nanoparticles and their integration into electronic devices, while also focusing on integrating them with 2D materials to improve device endurance and spin state detection.
ADVANCED MATERIALS
(2023)
Review
Chemistry, Physical
Saikat Mukherjee, Dmitry A. Fedorov, Sergey A. Varganov
Summary: This article reviews the application of nonadiabatic molecular dynamics methods in modeling spin-crossover transitions, focusing on different representations of electronic states, interstate couplings, and various NAMD methods used. Representative applications, as well as fundamental questions related to spin processes, are also discussed, with suggestions for future methodological developments in NAMD.
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, VOL 72
(2021)
Article
Chemistry, Inorganic & Nuclear
Nicolas Montenegro-Pohlhammer, Rocio Sanchez-de-Armas, Carmen J. Calzado, Merlys Borges-Martinez, Gloria Cardenas-Jiron
Summary: The study demonstrates that NiTP-PAPy strongly adsorbs on the Au(111) surface in both high spin and low spin configurations, and the photoinduced switching is preserved upon adsorption. DFT-NEGF calculations indicate that the current passing through the molecular junction-like systems is much higher in the high spin configuration, and the current in the ferromagnetic junction is highly spin-polarized.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Senthil Kumar Karuppannan, Alejandro Martin-Rodriguez, Eliseo Ruiz, Phimphaka Harding, David J. Harding, Xiaojiang Yu, Anton Tadich, Bruce Cowie, Dongchen Qi, Christian A. Nijhuis
Summary: This study reports the first room temperature switchable Fe(iii) molecular spin crossover tunnel junction, constructed from self-assembled molecules on graphene surfaces with conductance switching associated with the high and low spin states. Analysis reveals coherent tunnelling dominates charge transport across the molecule, and the SCO complex retains its functionality on the surface, indicating van der Waals molecule-electrode interfaces provide good junction stability while retaining SCO switching capability.
Article
Materials Science, Multidisciplinary
Miguel Gavara-Edo, Francisco Javier Valverde-Munoz, Rosa Cordoba, M. Carmen Munoz, Javier Herrero-Martin, Jose Antonio Real, Eugenio Coronado
Summary: In this study, three new neutral Fe(II) SCO molecules belonging to the {Fe[H2B(pz)(2)](2)(L)} family were synthesized, and their crystallographic structure and magnetic properties were investigated. These compounds exhibited thermal- and light-induced SCO transitions with different degrees of cooperativity and effectiveness. Furthermore, two of the compounds were demonstrated to be sublimable, forming homogeneous thin films that retained the chemical integrity of the original molecules. SCO/2D horizontal hybrid devices based on CVD-graphene were successfully produced using these films, enabling the detection of the thermal SCO transition through the electric properties of CVD-graphene.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Inorganic & Nuclear
Maksym Seredyuk, Kateryna Znovjyak, Francisco Javier Valverde-Munoz, M. Carmen Munoz, Volodymyr M. Amirkhanov, Igor O. Fritsky, Jose Antonio Real
Summary: This paper reports a series of neutral trans-thiocyanate mononuclear spin crossover complexes based on tetradentate ligands L. These complexes exhibit thermal-induced spin crossover behavior and the formation of photo-generated metastable high-spin phases.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Benjamin Le Ouay, Ryosuke Minami, Purna K. K. Boruah, Rin Kunitomo, Yuta Ohtsubo, Kohei Torikai, Ryo Ohtani, Cleimence Sicard, Masaaki Ohba
Summary: This study demonstrates the preparation of novel metal-organic polyhedra (MOPs) with anionic or cationic groups, which exhibit high affinity for proteins and can spontaneously form MOP-protein assemblies. The versatility of this method is illustrated using enzymes of different sizes and isoelectric points (pIs). The co-immobilization of cytochrome c with highly charged MOPs leads to a substantial increase in its catalytic activity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ryo Ohtani, Jianeng Xu, Junichi Yanagisawa, Yuudai Iwai, Takumi Ehara, Kiyoshi Miyata, Ken Onda, Jenny Pirillo, Yuh Hijikata, Tomoaki Hiraoka, Shinya Hayami, Benjamin Le Ouay, Masaaki Ohba
Summary: We synthesized an organic-inorganic hybrid material that undergoes drastic structural changes upon exposure to water vapor. The change in structure results in different photo-physical properties, with one form emitting near-infrared light and shifting to blue with increasing temperature, while the other form emits visible light and shifts to red.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Sven Johannsen, Manuel Gruber, Cyrille Barreteau, Maksym Seredyuk, Jose Antonio Real, Troels Markussen, Richard Berndt
Summary: The behavior of the neutral spin crossover complex Fe(neoim)(2) on Au and Ag (111) surfaces was investigated. It was found that the complex exhibits an electron-induced spin crossover on Ag(111) but fragments on Au. Density functional theory calculations revealed that the adsorbed complex is significantly distorted by interactions with the substrates, particularly van der Waals forces. Dispersion interaction also plays a crucial role in the relative stabilities of the low- and high-spin states of the adsorbed complex. The unexpected instability of the complex on the gold substrate is attributed to enhanced covalent bonding of the fragments to the substrate.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Alejandro Martinez Serra, Archit Dhingra, Maria Carmen Asensio, Jose Antonio Real, Juan Francisco Sanchez Royo
Summary: Temperature dependent X-ray photoemission spectroscopy (XPS) was used to study the spin-crossover (SCO) transition in the nanocrystals of 3D Hoffman-like {Fe(pz)[Pt(CN)(4)]}. The temperature-dependent variations in the Fe 2p core-level spectrum provide clear evidence of the spin-state transition in this SCO complex. The lack of discernible temperature-driven shifts in the binding energies of the N 1s core-level components may be due to the immunity of its HS electronic configuration to thermal fluctuations. The high-spin fraction versus temperature plot extracted from XPS measurements indicates that the surface of the nanocrystals of {Fe(pz)[Pt(CN)(4)]} is in the high-spin state at room temperature, making it promising for room-temperature spintronics and quantum information science applications.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Benjamin Le Ouay, Tomo Ohara, Ryosuke Minami, Rin Kunitomo, Ryo Ohtani, Masaaki Ohba
Summary: An efficient water-based purification strategy using commercially available centrifugal ultrafiltration membranes was developed for metal-organic polyhedra (MOPs). The MOPs, with a diameter above 3 nm, were retained by the filters while free ligands and impurities were washed away. The method also allowed for efficient counter-ion exchange, opening up possibilities for the application of MOPs in biological systems.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Alejandro Martinez Serra, Archit Dhingra, Maria Carmen Asensio, Jose Antonio Real, Juan Francisco Sanchez Royo
Summary: Temperature dependent X-ray photoemission spectroscopy (XPS) was used to study the Fe 2p and N 1s core levels of Fe(ii) spin crossover (SCO) complexes. The Fe 2p core-level spectra showed spin state transitions in these SCO complexes, consistent with previous studies. The temperature dependence of the N 1s core-level binding energy provided further insights into the ligand-to-metal charge transfer phenomenon.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Naoyuki Harada, Masanori Uji, Baljeet Singh, Nobuo Kimizuka, Nobuhiro Yanai
Summary: Researchers have achieved photon upconversion from visible light to ultraviolet light with a record-high efficiency of 27.6% by soaking a porous film in a low-volatile upconversion solution. Moreover, by combining this film with a microlens array, a significantly low threshold excitation light intensity of less than 0.60 mW cm-2, at least one order of magnitude lower than solar irradiance, is achieved.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Sumit Ranjan Maity, Monica Ceretti, Ruben De Barros, Lukas Keller, Juerg Schefer, Antonio Cervellino, J. Alberto Rodriguez Velamazan, Werner Paulus
Summary: In this study, the structural aspects of oxygen ion mobility diffusion mechanisms in non-stoichiometric Nd2NiO4+delta nickelates were investigated using X-ray and neutron diffraction. The temperature dependent synchrotron powder diffraction revealed a phase diagram of unprecedented complexity, involving highly organized, 3D modulated phases related to oxygen ordering below 800 K. The phase transitions imply translational periodicities exceeding 100 angstrom and are found to be of 1(st) order, with fast ordering kinetics. These surprising structural correlations, induced by the presence of interstitial oxygen atoms, suggest a collective phason-like oxygen diffusion mechanism together with dynamical contributions from the aperiodic lattice, creating shallow diffusion pathways down to room temperature.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Kana Orihashi, Akio Yamauchi, Saiya Fujiwara, Mizue Asada, Toshikazu Nakamura, Joseph Ka-Ho Hui, Nobuo Kimizuka, Kenichiro Tateishi, Tomohiro Uesaka, Nobuhiro Yanai
Summary: This study reports the achievement of spin-polarized radicals with extremely long spin-lattice relaxation times at room temperature in a metal-organic framework. The generation of persistent radicals through charge separation after photoexcitation and the successful transfer of spin polarization to these radicals have been demonstrated. This achievement in MOFs with nanopores accessible to guest molecules will play a significant role in highly sensitive quantum sensing and efficient dynamic nuclear polarization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Tomoyuki Hamachi, Koki Nishimura, Keita Sakamoto, Yusuke Kawashima, Hironori Kouno, Shunsuke Sato, Go Watanabe, Kenichiro Tateishi, Tomohiro Uesaka, Nobuhiro Yanai
Summary: This study demonstrates the successful triplet-DNP of pyruvate by utilizing supramolecular complexation with beta-cyclodextrin, which holds significant importance for the widespread use of ultra-sensitive MRI in cancer diagnosis.
Article
Chemistry, Physical
Miguel Gavara-Edo, Francisco Javier Valverde-Munoz, M. Carmen Munoz, Safaa Elidrissi Moubtassim, Francisco Marques-Moros, Javier Herrero-Martin, Kateryna Znovjyak, Maksym Seredyuk, Jose Antonio Real, Eugenio Coronado
Summary: Materials based on spin crossover molecules have attracted significant attention in molecular magnetism. This study presents a novel spin crossover material that can form thermally stable thin films while retaining its molecular bistability.
CHEMISTRY OF MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Alejandro Orellana-Silla, Manuel Meneses-Sanchez, Ruben Turo-Cortes, Victor Rubio-Gimenez, Giel Arnauts, M. Carmen Munoz, Rob Ameloot, Carlos Bartual-Murgui, Jose Antonio Real
Summary: Functionalization of spin crossover porous coordination polymers (PCPs) with hydrogen-bonding active groups is an efficient strategy for the study of multifunctional materials. The interaction of guests with the host framework can improve the cooperativity of the spin crossover (SCO) and further enhance its properties. Comprehensive magneto-structural studies are still needed to understand the role of guests in the enhancement of the SCO properties.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
