Article
Chemistry, Multidisciplinary
Maria Ksiazek, Marek Weselski, Marcin Kazmierczak, Aleksandra Polrolniczak, Andrzej Katrusiak, Damian Paliwoda, Joachim Kusz, Robert Bronisz
Summary: This article investigates the spin crossover phenomenon and its influencing factors in the coordination polymer [Fe(bbtr)(3)](BF4)(2). The spin crossover is very slow at low temperatures and is accompanied by a hysteresis loop. Unlike the perchlorate analogue, the tetrafluoroborate does not undergo a phase transition. The spin crossover temperature can be altered by applying pressure or heating. Single crystal X-ray diffraction studies reveal that the spin crossover mechanism is different under high pressure compared to thermal induction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Damian Paliwoda, Laure Vendier, Livia Getzner, Frederico Alabarse, Davide Comboni, Baptiste Martin, Seyed Ehsan Alavi, Mario Piedrahita Bello, Lionel Salmon, William Nicolazzi, Gabor Molnar, Azzedine Bousseksou
Summary: Two benchmark Fe(II)-triazole spin-crossover compounds, [Fe(Htrz)2trz]BF4 (1) and [Fe(NH2trz)3]SO4 (2), were investigated using various techniques to evaluate their transformation strain, compressibility, and anisotropy. Elastic softening and mechanical damping were observed during the spin-crossover process in both compounds, suggesting a coupling between spin state and lattice strain. The elastic potential energy, stored elastic work, and frictional work were assessed, providing important insights for understanding the behavior of this compound family and guiding their technological applications.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Maria Ksiazek, Marek Weselski, Joachim Kusz, Robert Bronisz
Summary: The coordination polymer formed by 1,4-Di(1,2,3-triazol-1-yl)butane and iron(ii) triflate exhibits unique spin crossover behavior for different iron(ii) ions at varying temperatures, along with structural transformation from R3 to P6(3) space group. The polymorphic system shows three crystallographically independent iron(ii) ions with a three-stage spin crossover process, despite a similar overall spin crossover behavior to the original crystal structure.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Yilv Guo, Xing Yu, Yehui Zhang, Xiwen Zhang, Shijun Yuan, Yafei Li, Shengyuan A. Yang, Jinlan Wang
Summary: This research proposes a new type of spin-constrained photoelectric memory using two-dimensional magnetic/ferroelectric heterostructures, which enables low-power electrical write operation and nondestructive optical read operation. The storage utilizes the polarization direction to alter the ferromagnetic and antiferromagnetic orderings in the magnetic layer, and records the spin-polarized/unpolarized current as the 1/0 state for logic processing and memory applications. First-principles calculations suggest that the NiI2/In2Se3 heterobilayer is an ideal candidate for such a spin-dependent photoelectric memory.
Article
Chemistry, Physical
Sven Johannsen, Sascha Schueddekopf, Sascha Ossinger, Jan Grunwald, Felix Tuczek, Manuel Gruber, Richard Berndt
Summary: Investigations were conducted on isolated tetramers of the spin crossover compound Fe(H2B-(pyrazole)(pyridylpyrazole))2on Ag(111) at cryogenic temperature using a scanning tunneling microscope (STM) in ultrahigh vacuum. Besides the spin states resulting from electron-induced spin crossover, a third state with distinct current-voltage characteristics and intramolecular image contrast was discovered. This state remains stable within a certain voltage range but decays into the low- and high-spin states of the Fe complex beyond that range. The researchers propose that this state corresponds to a negatively charged Fe complex in its high-spin state, which shares the same number of electrons with the analogous Co compound.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Materials Science, Multidisciplinary
Shiraz Ahmed Siddiqui, Oleg Domanov, Erhard Schafler, Jana Vejpravova, Hidetsugu Shiozawa
Summary: This study reports the synthesis of single crystals of iron-triazole coordination polymer and finds that the thermal spin crossover of the crystals depends largely on crystal size. Fine crystals are suitable for depositing thin films that exhibit redox activity, while the largest crystals allow reliable electrical conductance measurements.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
Article
Multidisciplinary Sciences
Maya Khela, Maciej Dabrowski, Safe Khan, Paul S. Keatley, Ivan Verzhbitskiy, Goki Eda, Robert J. Hicken, Hidekazu Kurebayashi, Elton J. G. Santos
Summary: In this study, the ability to generate different types of spin textures in the 2D van der Waals magnet CrGeTe3 and achieve reversible transformation between them using ultrafast laser excitation is demonstrated. Atomistic spin dynamics simulations and wide-field Kerr microscopy measurements show that high-intense laser pulses can generate different spin textures within the picosecond regime. The phase transformation between the different spin textures can be controlled by external magnetic fields through additional laser pulses. These results indicate the potential of laser-driven spin textures as a pathway to reconfigurable topological architectures at the atomistic level.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Xinyu Yang, Alejandro Enriquez-Cabrera, Dorian Toha, Yannick Coppel, Lionel Salmon, Azzedine Bousseksou
Summary: A pure mixed-anion Fe(NH(2)trz)(3)(BF4)(SiF6)(0.5) spin crossover complex is obtained through a solid-liquid post synthetic modification approach from the Fe(NH(2)trz)(3)(BF4)(2) parent complex. Highly crystalline powder samples incorporating homogeneous micrometric (1 & mu;m long) rod-shaped particles can be achieved using this method. This compound exhibits an abrupt spin crossover behavior with a narrow (10 K) hysteresis loop centered just above room temperature (320 K), making it highly interesting for integration into various application devices.
DALTON TRANSACTIONS
(2023)
Article
Polymer Science
K. Scanda, Y. Avila, R. Mojica, A. Cano, M. Gonzalez, J. Rodriguez-Hernandez, E. Reguera
Summary: The material crystallizes with an orthorhombic unit cell, its crystal structure was solved from powder XRD patterns. A reversible spin transition from high to low spin with hysteresis is observed, with the nitrosyl group playing a crucial role in tuning the bonding properties.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2022)
Article
Nanoscience & Nanotechnology
Jasneet Kaur, Adel Malekkhouyan, Gurpreet S. Selopal, Zhiming M. Wang, Federico Rosei, Hadis Zarrin
Summary: The functionalized hexagonal boron nitride (FhBN) nanoflakes with high proton conductivity were successfully synthesized and demonstrated excellent dispersibility and stability. When composed with Nafion solution, the FhBN-Nafion nanocomposite PEMs showed significantly improved proton conductivities in both in-plane and through-plane directions compared to pure Nafion, making it a promising material for electrochemical energy devices.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Multidisciplinary Sciences
Manoj K. Jana, Ruyi Song, Yi Xie, Rundong Zhao, Peter C. Sercel, Volker Blum, David B. Mitzi
Summary: A specific bond angle disparity connected with asymmetric tilting distortions of metal halide octahedra correlates with the computed spin-splitting in 2D hybrid perovskites. This distortion metric can serve as a crystallographic descriptor for rapidly discovering potential candidate materials with strong spin-splitting. Local inorganic layer distortions induced via appropriate organic cations provide a key design objective to achieve strong spin-splitting in perovskites.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Jialong Li, Xiaoxu Liu, Yu Feng, Dongyang Chen, Yanpeng Li, Dong Yue, Bingshun Huang, Jinghua Yin
Summary: Interfacial engineering, specifically core-shell architecture with highly insulating inorganic shell layer, is commonly used to enhance the energy storage density of polymer composites. However, the amorphous inorganic shell layer is usually the only option due to the interfacial tension caused by lattice mismatch. To overcome this limitation, bidirectional matched aluminum oxide interface transition regions were constructed between polyimide (PI) and Ca2Nb3O10 (CNO) nanosheets to prepare PI/CNO@AO composites. The successful construction of the bidirectional matched interface was confirmed through various experiments and characterizations, and it effectively suppressed carrier transportation and electric conduction in the composites, leading to excellent energy storage performance in both conventional and high-temperature environments.
ENERGY STORAGE MATERIALS
(2023)
Review
Physics, Multidisciplinary
Eric Collet, Giovanni Azzolina, Jelena Jeftic, Marie-Helene Lemee-Cailleau
Summary: We review different models developed to describe the thermal conversion process from low to high-spin states in spin-crossover (SCO) materials and the occurrence of cooperative conversions resulting from elastic interactions. There is a growing number of SCO materials exhibiting unusual thermal conversions when symmetry breaking occurs. To illustrate the importance of considering both phenomena, we review studies of the prototype [Fe(ptz)(6)](BF4)(2) system, which undergoes a single step thermal transition with hysteresis and shows a ferroelastic distortion from the high-spin high-symmetry (HShs) phase to the low-spin low-symmetry (LSls) phase at atmospheric pressure. Under pressure, sequential conversions occur on cooling from the HShs phase to a high-spin low-symmetry (HSls) phase, followed by a spin crossover towards the LSls phase.
ADVANCES IN PHYSICS-X
(2023)
Article
Chemistry, Physical
Xiaoxuan Ma, Rongrong Jia, Gang Zhao, Shuang Zhu, Wanting Yang, Wencheng Fan, Haiyang Chen, Baojuan Kang, Jin-Ke Bao, Shixun Cao
Summary: The introduction of Yb ions into SmFeO3 single crystal can modulate the spin reorientation transition temperature and enhance the magnetization compensation temperature. Different spin switching effects can be observed under applied magnetic fields, including a unique spin switching phenomenon at lower magnetic fields during room temperature spin reorientation.
JOURNAL OF ALLOYS AND COMPOUNDS
(2022)
Article
Materials Science, Multidisciplinary
Yuteng Zhang, Lijun Zhang, Karl Ridier, Lionel Salmon, Isabelle Seguy, Gabor Molnar, Azzedine Bousseksou
Summary: The study investigates the spin-state switching stability of the benchmark complex [Fe(HB(tz)(3))(2)] in different structures and confirms the intrinsic stability of certain spin crossover compounds; compared to ITO/[Zn(HB(tz)(3))(2)]/Al structures, the stability is mainly affected by the degradation of the device itself.
MATERIALS ADVANCES
(2022)
Article
Chemistry, Multidisciplinary
Johann Bosson, Geraldine M. Labrador, Celine Besnard, Denis Jacquemin, Jerome Lacour
Summary: By oxidizing tertiary alkyl amines to enamines and further reacting them to form donor-pi-acceptor coupling products, this synthetic approach extends conjugation, resulting in chromophores that absorb intensely in far-red or NIR domains. These chromophores also fluoresce in the NIR region, showing intense ECD properties with a |Delta epsilon| value up to 60 M^-1 cm^-1 around 790 nm.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Juan-Ramon Jimenez, Maxime Poncet, Sandra Miguez-Lago, Stephane Grass, Jerome Lacour, Celine Besnard, Juan M. Cuerva, Araceli G. Campana, Claude Piguet
Summary: Chiral CrIII complexes with dual circularly polarized luminescence in the near-infrared region have been successfully synthesized, providing potential applications for quantifying chiral targets in biological systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Kenji Caprice, David Pal, Celine Besnard, Bartomeu Galmes, Antonio Frontera, Fabien B. L. Cougnon
Summary: This study demonstrates the amplification of a mechanically chiral (P)-catenane by binding to (R)-1,1'-binaphthyl 2,2'-disulfonate, with a diastereomeric excess of 85%. The chirality of the [2]catenane was confirmed by single crystal X-ray diffraction and NMR/CD spectroscopies, establishing a basis for the development of new synthetic approaches to enantioenriched mechanically chiral [2]catenanes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Pavol Ondrisek, Margaux Elie, Marion Pupier, Adiran Aguirre, Amalia Poblador-Bahamonde, Celine Besnard, Jerome Lacour
Summary: In this study, the issue of loss of emissive properties in cationic compounds caused by the electron-donating groups (EDGs) is successfully addressed by introducing acetylene derivatives. Interestingly, a general dynamic stereoisomerism phenomenon is observed for the compounds derived from achiral DAOTA cores, attributed to the influence of the geometry of the side chains.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Julien Chong, Celine Besnard, Carlos M. Cruz, Claude Piguet, Juan-Ramon Jimenez
Summary: The substitution of water molecules around trivalent chromium with tridentate ligands results in the formation of [Cr(L)Br3] complexes, which can further react with other compounds under microwave irradiation. The deviation of six-coordinate [CrN3C3] chromophores from octahedral arrangement and the modulation of emission lifetimes at different temperatures are observed.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Pradip Chakraborty, Mouhamadou Sy, Houcem Fourati, Teresa Delgado, Mousumi Dutta, Chinmoy Das, Celine Besnard, Andreas Hauser, Cristian Enachescu, Kamel Boukheddaden
Summary: This study investigates the behavior of the spin crossover compound [Fe(ptz)(6)](BF4)(2) in the host lattice of [Ru(ptz)(6)](BF4)(2), revealing a decoupling between crystallographic phase transitions and thermal spin transitions. Dilution with Ru reduces the cooperative character of the transition and results in observed hysteretic thermal transitions with slight domain formation. The transition temperature is slightly dependent on crystal properties, emphasizing the importance of Ru spatial distribution in addition to crystal shape and size.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Yana Nikolova, Bibiana Fabri, Pau Moneva Lorente, Alejandro Guarnieri-Ibanez, Adiran de Aguirre, Yoshiki Soda, Gennaro Pescitelli, Francesco Zinna, Celine Besnard, Laure Guenee, Dimitri Moreau, Lorenzo Di Bari, Eric Bakker, Amalia Poblador-Bahamonde, Jerome Lacour
Summary: In this study, chiral quinacridines react multiple times with alpha-diazomalonates under Ru-II and Rh-II catalysis, achieving chemo and regioselective insertions of metal carbenes. This versatile method allows for the introduction of mono- or bis-functionalized malonate derivatives, which can be used to tune optical and chemical properties and for cellular bioimaging.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Frederic Foucher, Antonio Hrvat, Frances Westall, Celine Besnard, Guillaume Collet, Stephane Petoud
Summary: This study reports a new method of generating chiral structural hierarchy from nonchiral MOFs, and verifies the hypotheses through real-time optical microscopy observations.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Multidisciplinary
Hao Chen, Tian-Ren Li, Naomi Sakai, Celine Besnard, Laure Guenee, Marion Pupier, Jasmine Viger-Gravel, Konrad Tiefenbacher, Stefan Matile
Summary: This research introduces cascade cyclizations of diepoxides as a new tool for characterizing supramolecular catalysis. By decoding product fingerprints, the chemical selectivity, diastereo- and enantioselectivity, mechanism, and autocatalysis of substrate stereoisomers can be studied. The application of this tool to various supramolecular systems reveals interesting findings, such as pnictogen-bonding catalysis breaking the Baldwin rules and converting substrate diastereomers into completely different products.
Article
Chemistry, Multidisciplinary
Bumhee Lim, Takehiro Kato, Celine Besnard, Amalia I. Poblador Bahamonde, Naomi Sakai, Stefan Matile
Summary: This study expands the dynamic covalent chalcogen exchange cascades by inserting pnictogen relays and identifies privileged scaffolds for inhibiting cellular entry and viral infection.
Article
Chemistry, Multidisciplinary
Dorota Pulmannova, Celine Besnard, Petr Bezdicka, Marios Hadjimichael, Jeremie Teyssier, Enrico Giannini
Summary: Single crystals of transition metal oxides are crucial for studying their physical properties. In the strontium titanate family, crystal growth of all compounds except SrTiO3 has been challenging. This study successfully grew crystals of the high-temperature polymorph of Sr2TiO4 and investigated its crystal structure and transformation mechanism, providing insights into the failed growth of the low-temperature phase.
Article
Chemistry, Multidisciplinary
Guillaume Collet, Antonio Hrvat, Svetlana Eliseeva, Celine Besnard, Anton Kovalenko, Stephane Petoud
Summary: This study presents a lanthanide-based metal-organic framework (MOF) that emits near-infrared (NIR) light with Yb3+ sensitized by fluorescein (FL) as a low energy absorbing chromophore (FL@CD-MOF-161). The unique design of CD-MOF-161 allows for efficient loading and spreading of chromophores within the crystal volume, achieved by trapping FL molecules in its pores during synthesis and crystal growth.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Bahman Golesorkhi, Ines Taarit, Helene Bolvin, Homayoun Nozary, Juan-Ramon Jimenez, Celine Besnard, Laure Guenee, Alexandre Furstenberg, Claude Piguet
Summary: Certain chromophores found in complexes exhibit light upconversion processes, with quantum yields exceeding predicted values, possibly due to the excitation mechanism. Additionally, optimizing the upconversion mechanism is not crucial, with the dominant role of single-center erbium excited-state absorption process.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Alejandro Guarnieri-Ibanez, Adiran de Aguirre, Celine Besnard, Amalia Poblador-Bahamonde, Jerome Lacour
Summary: Hexahydropyrazinoindoles were prepared in a single step from N-sulfonyl triazoles and imidazolidines, using dirhodium catalysis to generate alpha-imino carbenes and nitrogen ylide intermediates. A regiodivergent reactivity was engineered through the use of a specific unsymmetrically substituted imidazolidine, leading to the exclusive formation of 8-membered ring 1,3,6-triazocines. Further derivatizations yielded functionalized tetrahydropyrazinoindoles in high yields, demonstrating an original Curtin-Hammett-like situation for the mechanism through DFT calculations.
Article
Chemistry, Inorganic & Nuclear
Neel Deorukhkar, Celine Besnard, Laure Guenee, Claude Piguet
Summary: The [FeN6] chromophores in [Fe(didentate)(3)](2+) complexes exhibit mixtures of C-1 and C-3 symmetry geometrical isomers, with alkyl-substituted six-membered heterocyclic rings controlling ligand field strength and electron delocalization. Specific ligand structures can lead to tunable thermally-induced spin transitions in solution, with differences observed between meridional and facial isomers. In solid-state, intermolecular interactions override minor thermodynamic trends seen in solution, leading to the predominance of a single configurational isomer.
DALTON TRANSACTIONS
(2021)
