Influence of Peripheral Substituents on Fe(II) Spin State in Complexes with Tridentate Schiff‐Base Ligands

Gakiya‐Teruya, Miguel; Le, Duy; Kumar, Divya; Jen, Natalie; Rydberg, Drake; Jo, Minyoung; Rahman, Talat; Shatruk, Michael

doi:10.1002/ejic.202400414

Title: Influence of Peripheral Substituents on Fe(II) Spin State in Complexes with Tridentate Schiff‐Base Ligands

Journal Article · 14 October 2024 · European Journal of Inorganic Chemistry

DOI: https://doi.org/10.1002/ejic.202400414 · OSTI ID:2477073

^[1]; Le, Duy ^[2]; Kumar, Divya ^[1];

^[1]; Rydberg, Drake ^[1]; Jo, Minyoung ^[1];

^[2];

^[1]

Department of Chemistry and Biochemistry Florida State University 95 Chieftan Way Tallahassee, FL 32306 USA
Department of Physics University of Central Florida 4111 Libra Dr Orlando, FL 32816 USA

Abstract Six Fe(II) complexes with substituted 6‐((quinoline‐8‐ylimino)methyl)phenolates (R ₂ qsal) were synthesized. X‐ray crystal structure determination for [Fe(R ₂ qsal) ₂ ], where R=F ( 1 ), Cl ( 2 ), Br ( 3 ), I ( 4 ), CF ₃ /H ( 5 ), or CN/H ( 6 ), revealed mononuclear complexes that crystallize either solvent‐free in case of 1 , 5 , and 6 or as CH ₂ Cl ₂ solvates in the case of 2 , 3 , and 4 . Complexes 1 – 4 , which contain π‐donating substituents, exhibit only high‐spin (HS) state, as shown by crystal structure analysis and magnetic measurements. In contrast, complexes 5 and 6 , which contain electron‐withdrawing substituents, exist in the low‐spin (LS) state at lower temperatures but exhibit crossover to the HS state above 300 K. Electronic structure calculations show a good correlation between the relative energies of the LS and HS states and the experimentally observed behavior.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0019330

OSTI ID:: 2477073

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 31 Vol. 27; ISSN 1434-1948

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (59)

Bistable Spin-Crossover Nanoparticles Showing Magnetic Thermal Hysteresis near Room Temperature Coronado, E.; Galán-Mascarós, J. R.; Monrabal-Capilla, M. Advanced Materials, Vol. 19, Issue 10 https://doi.org/10.1002/adma.200700559	journal	May 2007
Spin Crossover Probes Confer Multistability to Organic Conducting Polymers Koo, Yong-Sung; Galán-Mascarós, José Ramón Advanced Materials, Vol. 26, Issue 39 https://doi.org/10.1002/adma.201402579	journal	September 2014
Spin Crossover Nanomaterials: From Fundamental Concepts to Devices Molnár, Gábor; Rat, Sylvain; Salmon, Lionel Advanced Materials, Vol. 30, Issue 5 https://doi.org/10.1002/adma.201703862	journal	November 2017
Spin‐Crossover Molecules on Surfaces: From Isolated Molecules to Ultrathin Films Kipgen, Lalminthang; Bernien, Matthias; Tuczek, Felix Advanced Materials, Vol. 33, Issue 24 https://doi.org/10.1002/adma.202008141	journal	May 2021
Bistable Spin‐Crossover Nanoparticles for Molecular Electronics Torres‐Cavanillas, Ramón; Gavara‐Edo, Miguel; Coronado, Eugenio Advanced Materials, Vol. 36, Issue 1 https://doi.org/10.1002/adma.202307718	journal	October 2023
Single‐Molecule Spin Switch Based on Voltage‐Triggered Distortion of the Coordination Sphere Harzmann, Gero D.; Frisenda, Riccardo; van der Zant, Herre S. J. Angewandte Chemie International Edition, Vol. 54, Issue 45 https://doi.org/10.1002/anie.201505447	journal	November 2015
A Unified Treatment of the Relationship Between Ligand Substituents and Spin State in a Family of Iron(II) Complexes Kershaw Cook, Laurence J.; Kulmaczewski, Rafal; Mohammed, Rufeida Angewandte Chemie International Edition, Vol. 55, Issue 13 https://doi.org/10.1002/anie.201600165	journal	March 2016
A Bistable Microelectromechanical System Actuated by Spin-Crossover Molecules Manrique-Juarez, Maria D.; Mathieu, Fabrice; Shalabaeva, Victoria Angewandte Chemie International Edition, Vol. 56, Issue 28 https://doi.org/10.1002/anie.201702739	journal	May 2017
Sublimable Spin‐Crossover Complexes: From Spin‐State Switching to Molecular Devices Kumar, Kuppusamy Senthil; Ruben, Mario Angewandte Chemie International Edition, Vol. 60, Issue 14 https://doi.org/10.1002/anie.201911256	journal	October 2020
Effects of Substituents on Metastable‐State Photoacids: Design, Synthesis, and Evaluation of their Photochemical Properties Liu, Junning; Tang, Wenqi; Sheng, Lan Chemistry – An Asian Journal, Vol. 14, Issue 3 https://doi.org/10.1002/asia.201801687	journal	January 2019
Halogen Substitution Effects on N ₂ O Schiff Base Ligands in Unprecedented Abrupt Fe ^II Spin Crossover Complexes Phonsri, Wasinee; Macedo, David S.; Vignesh, Kuduva R. Chemistry - A European Journal, Vol. 23, Issue 29 https://doi.org/10.1002/chem.201700232	journal	May 2017
Quantitative Assessment of Ligand Substituent Effects on σ‐ and π‐Contributions to Fe−N Bonds in Spin Crossover Fe^IIComplexes Bondì, Luca; Garden, Anna L.; Totti, Federico Chemistry – A European Journal, Vol. 28, Issue 22 https://doi.org/10.1002/chem.202104314	journal	March 2022
Anionic Tuning of Spin Crossover in Fe^III–Quinolylsalicylaldiminate Complexes Sertphon, Darunee; Harding, David J.; Harding, Phimphaka European Journal of Inorganic Chemistry, Vol. 2013, Issue 5-6 https://doi.org/10.1002/ejic.201201066	journal	November 2012
Substituent‐Influenced Spin Crossover in Fe^III Quinolylsalicylaldiminates Sertphon, Darunee; Harding, David J.; Harding, Phimphaka European Journal of Inorganic Chemistry, Vol. 2016, Issue 3 https://doi.org/10.1002/ejic.201501188	journal	December 2015
Direct Visualization of Local Spin Transition Behaviors in Thin Molecular Films by Bimodal AFM Shalabaeva, Victoria; Bas, Alin‐Ciprian; Piedrahita‐Bello, Mario Small, Vol. 15, Issue 47 https://doi.org/10.1002/smll.201903892	journal	October 2019
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Surfaces, thin films and patterning of spin crossover compounds Mallah, Talal; Cavallini, Massimiliano Comptes Rendus Chimie, Vol. 21, Issue 12 https://doi.org/10.1016/j.crci.2018.02.007	journal	December 2018
Metal complexes driven from Schiff bases and semicarbazones for biomedical and allied applications: a review More, M. S.; Joshi, P. G.; Mishra, Y. K. Materials Today Chemistry, Vol. 14 https://doi.org/10.1016/j.mtchem.2019.100195	journal	December 2019
Imidazole Schiff base ligands: Synthesis, coordination complexes and biological activities McGinley, John; McCann, Malachy; Ni, Kaijie Polyhedron, Vol. 55 https://doi.org/10.1016/j.poly.2013.03.023	journal	May 2013
Variety of spin transition temperatures of iron(II) spin crossover complexes with halogen substituted Schiff-base ligands, Hqsal X (X = F, Cl, Br, and I) Kuroda-Sowa, Takayoshi; Isobe, Rina; Yamao, Norifumi Polyhedron, Vol. 136 https://doi.org/10.1016/j.poly.2017.03.007	journal	November 2017
Visualization of Weak Interaction Effects on N₂O Schiff Base Ligands in Iron(II) Spin Crossover Complexes Sugimoto, Kunihisa; Okubo, Takashi; Maekawa, Masahiko Crystal Growth & Design, Vol. 21, Issue 7 https://doi.org/10.1021/acs.cgd.1c00426	journal	June 2021
Design and Processing as Ultrathin Films of a Sublimable Iron(II) Spin Crossover Material Exhibiting Efficient and Fast Light-Induced Spin Transition Gavara-Edo, Miguel; Valverde-Muñoz, Francisco Javier; Muñoz, M. Carmen Chemistry of Materials, Vol. 35, Issue 22 https://doi.org/10.1021/acs.chemmater.3c01704	journal	November 2023
Spin Crossover in Iron(III) Quinolylsalicylaldiminates: The Curious Case of [Fe(qsal-F)₂](Anion) Díaz-Torres, Raúl; Phonsri, Wasinee; Murray, Keith S. Inorganic Chemistry, Vol. 59, Issue 18 https://doi.org/10.1021/acs.inorgchem.0c02201	journal	September 2020
Anion Modified Spin Crossover in [Fe(qsal-4-F)]⁺ Complexes with a 4-Position Substituted Qsal Ligand Sheng, Hui-Juan; Xia, Cheng-Cai; Zhang, Xin-Yu Inorganic Chemistry, Vol. 61, Issue 32 https://doi.org/10.1021/acs.inorgchem.2c01795	journal	July 2022
Intermolecular Interaction Tuning of Spin-Crossover Iron(III) Complexes with Aromatic Counteranions Tsukiashi, Asami; Nakaya, Manabu; Kobayashi, Fumiya Inorganic Chemistry, Vol. 57, Issue 5 https://doi.org/10.1021/acs.inorgchem.7b03126	journal	February 2018
Synthesis and Characterization of Metal Complexes with Schiff Base Ligands Wilkinson, Shane M.; Sheedy, Timothy M.; New, Elizabeth J. Journal of Chemical Education, Vol. 93, Issue 2 https://doi.org/10.1021/acs.jchemed.5b00555	journal	December 2015
Quantitative Study of the Energy Changes in Voltage-Controlled Spin Crossover Molecular Thin Films Mosey, Aaron; Dale, Ashley S.; Hao, Guanhua The Journal of Physical Chemistry Letters, Vol. 11, Issue 19 https://doi.org/10.1021/acs.jpclett.0c02209	journal	September 2020
Phase Transitions in Spin-Crossover Thin Films Probed by Graphene Transport Measurements Dugay, J.; Aarts, M.; Giménez-Marqués, M. Nano Letters, Vol. 17, Issue 1 https://doi.org/10.1021/acs.nanolett.6b03780	journal	December 2016
Design and Synthesis of Tranylcypromine-Derived LSD1 Inhibitors with Improved hERG and Microsomal Stability Profiles Koda, Yasuko; Sato, Shin; Yamamoto, Hirofumi ACS Medicinal Chemistry Letters, Vol. 13, Issue 5 https://doi.org/10.1021/acsmedchemlett.2c00120	journal	April 2022
Diamagnetic Corrections and Pascal's Constants Bain, Gordon A.; Berry, John F. Journal of Chemical Education, Vol. 85, Issue 4 https://doi.org/10.1021/ed085p532	journal	April 2008
Coordination Chemistry of a π-Extended, Rigid and Redox-Active Tetrathiafulvalene-Fused Schiff-Base Ligand Wu, Jin-Cai; Liu, Shi-Xia; Keene, Tony D. Inorganic Chemistry, Vol. 47, Issue 8 https://doi.org/10.1021/ic800138x	journal	April 2008
Properties of Prussian Blue Materials Manifested in Molecular Complexes: Observation of Cyanide Linkage Isomerism and Spin-Crossover Behavior in Pentanuclear Cyanide Clusters Shatruk, Mikhail; Dragulescu-Andrasi, Alina; Chambers, Kristen E. Journal of the American Chemical Society, Vol. 129, Issue 19 https://doi.org/10.1021/ja066273x	journal	May 2007
Surface Plasmons Reveal Spin Crossover in Nanometric Layers Félix, Gautier; Abdul-Kader, Khaldoun; Mahfoud, Tarik Journal of the American Chemical Society, Vol. 133, Issue 39 https://doi.org/10.1021/ja207196b	journal	September 2011
Asymmetric Design of Spin-Crossover Complexes to Increase the Volatility for Surface Deposition Gakiya-Teruya, Miguel; Jiang, Xuanyuan; Le, Duy Journal of the American Chemical Society, Vol. 143, Issue 36 https://doi.org/10.1021/jacs.1c04598	journal	September 2021
A Simple Approach for Predicting the Spin State of Homoleptic Fe(II) Tris-diimine Complexes Phan, Hoa; Hrudka, Jeremy J.; Igimbayeva, Dilyara Journal of the American Chemical Society, Vol. 139, Issue 18 https://doi.org/10.1021/jacs.7b02098	journal	April 2017
Single-nanoparticle phase transitions visualized by four-dimensional electron microscopy van der Veen, Renske M.; Kwon, Oh-Hoon; Tissot, Antoine Nature Chemistry, Vol. 5, Issue 5 https://doi.org/10.1038/nchem.1622	journal	April 2013
Ultrafast carbon monoxide photolysis and heme spin-crossover in myoglobin via nonadiabatic quantum dynamics Falahati, Konstantin; Tamura, Hiroyuki; Burghardt, Irene Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06615-1	journal	October 2018
Femtosecond X-ray emission study of the spin cross-over dynamics in haem proteins Kinschel, Dominik; Bacellar, Camila; Cannelli, Oliviero Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17923-w	journal	August 2020
Seismological expression of the iron spin crossover in ferropericlase in the Earth’s lower mantle Shephard, Grace E.; Houser, Christine; Hernlund, John W. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26115-z	journal	October 2021
Thickness-dependent spin bistable transitions in single-crystalline molecular 2D material Koptur-Palenchar, John; Gakiya-Teruya, Miguel; Le, Duy npj 2D Materials and Applications, Vol. 6, Issue 1 https://doi.org/10.1038/s41699-022-00335-3	journal	September 2022
Single-molecule quantum-transport phenomena in break junctions Gehring, Pascal; Thijssen, Jos M.; van der Zant, Herre S. J. Nature Reviews Physics, Vol. 1, Issue 6 https://doi.org/10.1038/s42254-019-0055-1	journal	May 2019
Spin-state modulation of molecular Fe^III complexes via inclusion in halogen-bonded supramolecular networks Jeon, Ie-Rang; Jeannin, Olivier; Clérac, Rodolphe Chemical Communications, Vol. 53, Issue 36 https://doi.org/10.1039/C7CC01943B	journal	January 2017
Spin-state dependent conductance switching in single molecule-graphene junctions Burzurí, Enrique; García-Fuente, Amador; García-Suárez, Victor Nanoscale, Vol. 10, Issue 17 https://doi.org/10.1039/C8NR00261D	journal	January 2018
Thermal and light-induced spin transition in a nanometric film of a new high-vacuum processable spin crossover complex Atzori, Matteo; Poggini, Lorenzo; Squillantini, Lorenzo Journal of Materials Chemistry C, Vol. 6, Issue 33 https://doi.org/10.1039/C8TC02685H	journal	January 2018
Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale Rubio-Giménez, Víctor; Tatay, Sergio; Martí-Gastaldo, Carlos Chemical Society Reviews, Vol. 49, Issue 15 https://doi.org/10.1039/C9CS00594C	journal	January 2020
Spin-crossover in iron( ii )-Schiff base complexes Senthil Kumar, Kuppusamy; Bayeh, Yosef; Gebretsadik, Tesfay Dalton Transactions, Vol. 48, Issue 41 https://doi.org/10.1039/C9DT02085C	journal	January 2019
Room temperature conductance switching in a molecular iron(iii) spin crossover junction Karuppannan, Senthil Kumar; Martín-Rodríguez, Alejandro; Ruiz, Eliseo Chemical Science, Vol. 12, Issue 7 https://doi.org/10.1039/D0SC04555A	journal	January 2021
Structural and theoretical insights into solvent effects in an iron(iii) SCO complex Díaz-Torres, Raúl; Boonprab, Theerapoom; Gómez-Coca, Silvia Inorganic Chemistry Frontiers, Vol. 9, Issue 20 https://doi.org/10.1039/D2QI01159J	journal	January 2022
Mononuclear Fe(iii) complexes with 2,4-dichloro-6-((quinoline-8-ylimino)methyl)phenolate: synthesis, structure, and magnetic behavior Jeong, Ah Rim; Park, Si Ra; Shin, Jong Won Dalton Transactions, Vol. 53, Issue 15 https://doi.org/10.1039/D3DT04385A	journal	January 2024
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Anomalous compressibility of ferropericlase throughout the iron spin cross-over Wentzcovitch, R. M.; Justo, J. F.; Wu, Z. Proceedings of the National Academy of Sciences, Vol. 106, Issue 21 https://doi.org/10.1073/pnas.0812150106	journal	May 2009
On stabilizing spin crossover molecule [Fe(tBu₂qsal)₂] on suitable supports: insights from ab initio studies Le, Duy; Jiang, Tao; Gakiya-Teruya, Miguel Journal of Physics: Condensed Matter, Vol. 33, Issue 38 https://doi.org/10.1088/1361-648X/ac0beb	journal	July 2021
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
Elasticity of (Mg,Fe)O Through the Spin Transition of Iron in the Lower Mantle Crowhurst, J. C.; Brown, J. M.; Goncharov, A. F. Science, Vol. 319, Issue 5862 https://doi.org/10.1126/science.1149606	journal	January 2008
Nonvolatile Voltage Controlled Molecular Spin-State Switching for Memory Applications Ekanayaka, Thilini K.; Hao, Guanhua; Mosey, Aaron Magnetochemistry, Vol. 7, Issue 3 https://doi.org/10.3390/magnetochemistry7030037	journal	March 2021

Similar Records

Homoleptic versus Heteroleptic Formation of Mononuclear Fe(II) Complexes with Tris-Imine Ligands

Journal Article · 2016 · Inorganic Chemistry · OSTI ID:1439199

Barrios, Leoni A.; Bartual-Murgui, Carlos; Peyrecave-Lleixa, Eugenia; +4 more

Guest-, Light- and Thermally-Modulated Spin Crossover in [Fe^II₂] Supramolecular Helicates

Journal Article · 2016 · Chemistry - A European Journal · OSTI ID:1459362

Darawsheh, Mohanad; Barrios, Leoni A.; Roubeau, Olivier; +2 more

High-temperature spin transition in coordination compounds of iron(II) with triazoles

Journal Article · 1986 · Sov. J. Coordinat. Chem.; (United States) · OSTI ID:6158292

Lavrenova, L G; Ikorskii, V N; Varnek, V A; +2 more

Title: Influence of Peripheral Substituents on Fe(II) Spin State in Complexes with Tridentate Schiff‐Base Ligands

Citation Formats

References (59)

Similar Records

Related Subjects