Article
Chemistry, Physical
William G. Whitehurst, Junho Kim, Stefan G. Koenig, Paul J. Chirik
Summary: The cationic bis(phosphine) cobalt(I) arene complex was studied as a precatalyst for the three-component coupling reaction. However, hydrovinylation from the alkene and alkyne was favored over three-component coupling, indicating the role of C-H activation. Deuterium labeling supported the mechanism involving β-H elimination from a putative cobalt(III)-alkyl,aryl intermediate formed after C-H activation. The selectivity of C(sp(3))-C(sp(2)) reductive elimination versus β-H elimination from the cobalt(III)-alkyl,aryl intermediate was determined by varying the arene and alkene coupling partners.
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
Materials Science, Multidisciplinary
Margaux Penicaud, Edoardo Martinez, Giulia Serrano, Brunetto Cortigiani, Lorenzo Squillantini, Juan H. Gonzalez-Estefan, Emilio Velez-Fort, Mathieu Duttine, Mathieu Gonidec, Patrick Rosa, Matteo Mannini, Lorenzo Poggini
Summary: A new spin-crossover complex based on a heteroscorpionate ligand was synthesized and characterized. Thin films were grown on HOPG and Au(111) surfaces, and their properties were studied using X-ray absorption and X-ray photoemission spectroscopy. The results showed that the thermally induced spin-crossover is preserved at a sub-monolayer coverage on HOPG, while it is lost on Au(111) surface.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
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, Inorganic & Nuclear
Alexander R. Craze, Hikaru Zenno, Michael C. Pfrunder, John C. McMurtrie, Shinya Hayami, Jack K. Clegg, Feng Li
Summary: This study investigates the interaction between crystal packing, intermolecular interactions, and the magnetic behavior of SCO materials. The research found that a more separated array of SCO units leads to more extensive spin-transitions, while a tightly arranged lattice environment stabilizes the low-spin state.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Maite Noessler, Rene Jaeger, David Hunger, Marc Reimann, Tobias Bens, Nicolas I. Neuman, Arijit Singha Hazari, Martin Kaupp, Joris van Slageren, Biprajit Sarkar
Summary: Due to their ability to form stable molecular complexes, terpyridine ligands with tailor-made properties are of great interest in chemistry and material science. By synthesizing two terpyridine ligands with different fluorinated phenyl rings, we were able to prepare Co-II and Fe-II complexes and investigate their properties using various analytical techniques. Our findings revealed the structural characteristics, electrochemical behavior, and magnetic properties of these complexes, providing valuable insights into their applications and potential uses.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Yue Zhou, Xiao-Qin Wei, Ying Gu, Qi-Qi Zhao, Dong Shao
Summary: We present the syntheses, crystal structures, and spin crossover properties of a series of halogen-functionalized cobalt(II) complexes. The packing structures of these complexes were tuned by varying organosulfonates. The spin crossover properties were significantly influenced by the supramolecular packing structures, internal pressure, and structural distortion of the complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(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
Chemistry, Multidisciplinary
Yong-Xian Huang, Hua-Juan Hu, Rong-Jia Wei, Guo-Hong Ning, Dan Li
Summary: This study prepared an analogous complex and obtained a series of crystalline polymorphs with different packing modes and intermolecular interactions. By comparing different ligands, it was found that the NCSe- ligand showed a stronger ligand-field strength and weaker cooperativity compared to NCS-, resulting in a critical shift of T-1/2 values and a more gradual transition process.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Chemistry, Multidisciplinary
Sriram Sundaresan, Jonathan Kiehl, Luca M. Carrella, Eva Rentschler
Summary: We synthesized a thiadiazole based ligand with a methoxy substituent in the sixposition of the naphthalene ring, along with its corresponding iron(II) complexes. The complexes were characterized and it was found that complex 1 shows a weak thermally induced excited spin state trapping effect. The effects of the methoxy ligand substituent in altering the noncovalent intramolecular interaction and the tuning of the switching temperature by the choice of NCE were discussed.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Tobias Paschelke, Eicke Trumpf, David Grantz, Malte Pankau, Niclas Grocholski, Christian Naether, Frank D. Soennichsen, Anna J. Mcconnell
Summary: In this study, a family of (Fe4L6)-L-II spin-crossover cages based on 2,2'-pyridylbenzimidazoles was reported, and it was found that subtle ligand modifications can lower the spin crossover temperature in CD3CN by up to 186 K. Comparing different pairs of cages, it was observed that CH3 substituents on either the coordination motif or phenylene linker can lower the spin-crossover temperature by different degrees, attributed to electronic effects, steric effects, and a combination of both. The understanding of the interplay between ligand modifications from this study could contribute to the improved rational design of spin-crossover cages.
DALTON TRANSACTIONS
(2023)
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)
Article
Chemistry, Multidisciplinary
Mario Palacios-Corella, Javier Ramos-Soriano, Manuel Souto, Duarte Ananias, Joaquin Calbo, Enrique Orti, Beatriz M. Illescas, Miguel Clemente-Leon, Nazario Martin, Eugenio Coronado
Summary: This study designed and synthesized a family of hexakis-substituted [60]fullerene adducts with a well-known ligand for spin-crossover systems. Experimental and theoretical evidence showed that these molecular scaffolds can form polynuclear SCO complexes in solution, and retain SCO properties in the solid state.
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)
Review
Chemistry, Inorganic & Nuclear
Ke Sun, Jin-Peng Xue, Zi-Shuo Yao, Jun Tao
Summary: In this perspective, we briefly review the main synthetic strategies and progresses in fluorescent spin-crossover (SCO) materials in the last twenty years, emphasizing the promising applications of fluorescent SCO bifunctional materials in magneto-optical switching and information processing.
DALTON TRANSACTIONS
(2022)