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, Multidisciplinary
Malte Oppermann, Francesco Zinna, Jerome Lacour, Majed Chergui
Summary: This study demonstrates trapping of the high-spin state in iron-based spin-crossover complexes by controlling the chiral configuration. The high-spin-state decay is found to be accompanied by changes in optical activity, reflecting coupling to a symmetry-breaking torsional mode. Diastereoselective ion pairing suppresses vibrational population and increases the high-spin-state lifetime. These findings motivate the synthetic control of torsional modes in iron(II) complexes to manipulate their spin-crossover dynamics as a complementary approach.
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, 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, Inorganic & Nuclear
Zhi-Jian Ouyang, Xiao-Ying Mo, Jia-Qi Ye, Xiao-Xuan Yu, Shu-Yuan Huang, Xiao-Ling Liu, Wen-Bin Chen, Song Gao, Wen Dong
Summary: Two ion-pair Fe(iii) complexes were synthesized by employing the tridentate ligand H(3)ATD, with one in low-spin state and the other undergoing high temperature spin crossover between 360 and 500 K. The magnetic measurements and magneto-structural relationship studies reveal the crucial role of interactions between the cation and anion in the high temperature Fe(iii) behavior.
DALTON TRANSACTIONS
(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)
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)
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
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
Ismael Francisco Diaz-Ortega, Eva Luz Fernandez-Barbosa, Silvia Titos-Padilla, Simon J. A. Pope, Juan-Ramon Jimenez, Enrique Colacio, Juan Manuel Herrera
Summary: Nanoparticles based on polymer were prepared, with the silica-coated ones showing enhanced abruptness of spin transition. A Re(I) complex with intense green emission was synthesized, and its grafting onto the silica shell led to a bifunctional SCO-luminescence composite whose properties were tuned by spin state switching. Photophysical studies demonstrated synchronized luminescence and spin transition through a radiative energy transfer mechanism between different centers.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Brian A. Finney, Sabyasachi Roy Chowdhury, Clara Kirkvold, Bess Vlaisavljevich
Summary: By using fully internally contracted (FIC)-CASPT2 analytical gradients, geometry optimizations of spin-crossover complexes have been reported. The study shows that a wave function-based level of theory can be used to optimize the geometries of metal complexes in reasonable times and enable treatment of the molecular geometry and electronic structure of the complexes at the same level of theory. Good overall agreement between DFT and CASPT2 was observed, especially for larger complexes with moderate sized basis sets. Based on efficiency, the recommendation is to use the (10e,12o) active space for convergence to a minimum structure.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Vyshnavi Vennelakanti, Michael G. Taylor, Aditya Nandy, Chenru Duan, Heather J. Kulik
Summary: In this study, the electronic and Gibbs free energies associated with spin crossover in 95 Fe(II) SCO complexes were investigated using density functional theory (DFT) with 30 different functionals. It was found that a modified version of B3LYP, M06-L, and TPSSh functionals accurately predict the spin crossover behavior of most complexes, while the MN15-L functional fails to predict any spin crossover behavior.
JOURNAL OF CHEMICAL PHYSICS
(2023)
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
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, Multidisciplinary
Bryan C. Paulus, Karl C. Nielsen, Christopher R. Tichnell, Monica C. Carey, James K. McCusker
Summary: The development of chromophores based on earth-abundant transition metals with charge-transfer excited states has led to significant research. A new heteroleptic compositional motif was explored to combine strong ligand field and chemical tunability into a single compound. Spectroscopic measurements and ultrafast electronic absorption measurements revealed differences in excited state lifetimes and kinetics for the newly synthesized compound, highlighting the importance for designing compounds with specific optical properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Nicolas P. E. Barry, Anais Pitto-Barry, Johanna Tran, Simon E. F. Spencer, Adam M. Johansen, Ana M. Sanchez, Andrew P. Dove, Rachel K. O'Reilly, Robert J. Deeth, Richard Beanland, Peter J. Sadler
CHEMISTRY OF MATERIALS
(2015)
Article
Chemistry, Multidisciplinary
Laurence J. Kershaw Cook, Rafal Kulmaczewski, Rufeida Mohammed, Stephen Dudley, Simon A. Barrett, Marc A. Little, Robert J. Deeth, Malcolm A. Halcrow
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2016)
Article
Chemistry, Inorganic & Nuclear
K. A. H. Alzahrani, R. J. Deeth
DALTON TRANSACTIONS
(2016)
Article
Chemistry, Inorganic & Nuclear
Hong-Ke Liu, Hana Kostrhunova, Abraha Habtemariam, Yaqiong Kong, Robert J. Deeth, Viktor Brabec, Peter J. Sadler
DALTON TRANSACTIONS
(2016)
Article
Chemistry, Physical
Matthew Turner, James A. Platts, Robert J. Deeth
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2016)
Article
Biochemistry & Molecular Biology
Khalid A. H. Alzahrani, Robert J. Deeth
JOURNAL OF MOLECULAR MODELING
(2016)
Article
Chemistry, Inorganic & Nuclear
Silvia Amabilino, Robert J. Deeth
INORGANIC CHEMISTRY
(2017)
Article
Biochemistry & Molecular Biology
Shaun T. Mutter, Robert J. Deeth, Matthew Turner, James A. Platts
JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS
(2018)
Article
Biochemistry & Molecular Biology
Matthew Turner, Robert J. Deeth, James A. Platts
JOURNAL OF INORGANIC BIOCHEMISTRY
(2017)
Article
Chemistry, Inorganic & Nuclear
Marina Cendic, Robert J. Deeth, Auke Meetsma, Eugenio Garribba, Daniele Sanna, Zoran D. Matovic
Article
Chemistry, Multidisciplinary
V. Venkatesh, Raul Berrocal-Martin, Christopher J. Wedge, Isolda Romero-Canelon, Carlos Sanchez-Cano, Ji-Inn Song, James P. C. Coverdale, Pingyu Zhang, Guy J. Clarkson, Abraha Habtemariam, Steven W. Magennis, Robert J. Deeth, Peter J. Sadler
Article
Biochemistry & Molecular Biology
Shaun T. Mutter, Matthew Turner, Robert J. Deeth, James A. Platts
ACS CHEMICAL NEUROSCIENCE
(2018)
Article
Chemistry, Multidisciplinary
Paul V. Bernhardt, Jessica K. Bilyj, Victor Brosius, Dmitry Chernyshov, Robert J. Deeth, Marco Foscato, Vidar R. Jensen, Nicole Mertes, Mark J. Riley, Karl W. Tornroos
CHEMISTRY-A EUROPEAN JOURNAL
(2018)
Article
Multidisciplinary Sciences
Matthew Turner, Shaun T. Mutter, Robert J. Deeth, James A. Platts
Article
Chemistry, Multidisciplinary
Robert J. Deeth, Malcolm A. Halcrow, Laurence J. Kershaw Cook, Paul R. Raithby
CHEMISTRY-A EUROPEAN JOURNAL
(2018)