Spin modification of iron(ii) complexes via covalent (dative) and dispersion guided non-covalent bonding with N-heterocyclic carbenes: DFT, DLPNO-CCSD(T) and MCSCF studies

2020 ◽  
Vol 49 (1) ◽  
pp. 164-170
Author(s):  
Debashree Manna ◽  
Rabindranath Lo ◽  
Pavel Hobza
Keyword(s):  
High Spin ◽  
Spin Crossover ◽  
Covalent Bonding ◽  
Heterocyclic Carbenes ◽  
Covalent Interaction ◽  
Intermediate Spin

Spin crossover from high spin Fe(ii)-phthalocyanine to low or intermediate spin via either dative covalent or non-covalent interaction by just varying the substituent using the same core ligand.

The Flexibility of Long Chain Substituents Influences Spin-Crossover in Isomorphous Lipid Bilayer Crystals

2021 ◽  
Author(s):  
Iurii Galadzhun ◽  
Rafal Kulmaczewski ◽  
Namrah Shahid ◽  
Oscar Cespedes ◽  
Mark J Howard ◽  
...  
Keyword(s):  
Lipid Bilayer ◽  
High Spin ◽  
Room Temperature ◽  
Spin Crossover ◽  
Pyridine Derivatives ◽  
Long Chain

[Fe(bpp)2][BF4]2 (bpp = 2,6-di{pyrazol-1-yl}pyridine) derivatives bearing a bent geometry of hexadec-1-ynyl or hexadecyl substituents pyrazole are isomorphous, and high-spin at room temperature. However, only the latter compound undergoes an abrupt,...

MO-Theoretical Studies on a Model Complex for Deoxymyoglobin

1998 ◽  
Vol 53 (9) ◽  
pp. 755-765
Author(s):  
Christian Kollma ◽  
Sighart F. Fischer ◽  
Michael C. Böhm
Keyword(s):  
High Spin ◽  
Ground State ◽  
High Spin State ◽  
Open Shell ◽  
Spin States ◽  
Hartree Fock ◽  
Intermediate Spin ◽  
Model Complex ◽  
Out Of Plane ◽  
Overlap Method

AbstractThe origin of the displacement of the Fe atom in deoxymyoglobin with respect to the porphyrin plane in the high-spin state is examined by a qualitative molecular orbital (MO) analysis on the extended Hückel level. We find that attachment of a fifth ligand (imidazole in our model complex) to Fe(II)porphyrin favors the out-of-plane shift due to a strengthening of the bonding interaction between Fe and the nitrogen of the imidazole ligand. This results in a high-spin (5 = 2) ground state with Fe shifted out-of-plane for the five-coordinate complex instead of an intermediate spin ground state (5 = 1) with Fe lying in the plane for four-coordinate Fe(II)porphyrin. The relative energies of the different spin states as a function of the distance between Fe and the porphyrin plane are evaluated using an ROHF (restricted open shell Hartree-Fock) version of an INDO (intermediate neglect of differential overlap) method. We observe a level crossing between high-spin and intermediate spin states whereas the low-spin (5 = 0) state remains always higher in energy.

Large- Scale ab initio Simulations of Fe-doped SrTiO3 Perovskites

2002 ◽  
Vol 731 ◽  
Author(s):  
R.A. Evarestov ◽  
R.I. Eglitis ◽  
S. Piskunov ◽  
E. A. Kotomin ◽  
G. Borstel
Keyword(s):  
Energy Level ◽  
Ab Initio ◽  
High Spin ◽  
Spin State ◽  
Large Scale ◽  
Covalent Bonding ◽  
Hartree Fock ◽  
Ab Initio Simulations ◽  
Displacement Mode ◽  
Jahn Teller

AbstractUsing the Unrestricted Hartree-Fock method and supercells containing up to 160 atoms, we calculated the energy level positions in the gap and atomic geometry for the Fe4+ impurity substituting for a host Ti atom in SrTiO3. In agreement with experiment, the high spin (S=2) state is much lower in energy than the zero-spin state. The energy level positions strongly depend on the asymmetric displacement mode of the six nearest O ions which is a combination of the Jahn-Teller and breathing modes. A considerable covalent bonding between the Fe ion and four nearest O ions takes place.

Optical Microscopy Imaging of the Thermally-Induced Spin Transition and Isothermal Multi-stepped Relaxation in a Low-Spin Stabilized Spin-Crossover Material

2021 ◽  
Author(s):  
Pradip Chakraborty ◽  
Mouhamadou Sy ◽  
Houcem Fourati ◽  
Maria Teresa Delgado Pérez ◽  
Mousumi Dutta ◽  
...  
Keyword(s):  
Optical Microscopy ◽  
High Spin ◽  
Spin Relaxation ◽  
Spin Crossover ◽  
Spin Transition ◽  
Host Lattice ◽  
Microscopy Imaging ◽  
Thermally Induced ◽  
Optical Microscopy Imaging

The thermal spin transition and the photo-induced high-spin → low-spin relaxation of the prototypical [Fe(ptz)6](BF4)2 spin-crossover compound (ptz = 1-propyltetrazole) diluted in the isostructural ruthenium host lattice [Ru(ptz)6](BF4)2, which stabilizes...

Light-Induced Spin Crossover in an Intermediate-Spin Penta-Coordinated Iron(III) Complex

2019 ◽  
Vol 123 (46) ◽  
pp. 9883-9892 ◽  
Author(s):  
Sabyasachi Roy Chowdhury ◽  
Sabyashachi Mishra
Keyword(s):  
Spin Crossover ◽  
Intermediate Spin

scholarly journals Spin Crossover between the High-Spin and Low-Spin States and Dielectric Switching in the Ionic Crystals of a Fe(II) [2 × 2] Molecular Grid

2020 ◽  
Vol 93 (12) ◽  
pp. 1583-1587
Author(s):  
Yuta Uezu ◽  
Ryo Tsunashima ◽  
Chiaki Tanaka ◽  
Masaru Fujibayashi ◽  
Jun Manabe ◽  
...  
Keyword(s):  
High Spin ◽  
Spin Crossover ◽  
Spin States ◽  
Ionic Crystals

scholarly journals Adsorption of iron tetraphenylporphyrin on (111) surfaces of coinage metals: a density functional theory study

2017 ◽  
Vol 8 ◽  
pp. 2484-2491 ◽  
Author(s):  
Hao Tang ◽  
Nathalie Tarrat ◽  
Véronique Langlais ◽  
Yongfeng Wang
Keyword(s):  
Density Functional Theory ◽  
High Spin ◽  
Density Functional ◽  
Activation Barrier ◽  
High Spin State ◽  
Coulomb Repulsion ◽  
Functional Theory ◽  
Adsorption Sites ◽  
Intermediate Spin ◽  
Magnetic States

The adsorption of the iron tetraphenylporphyrin (FeTPP) molecule in its deckchair conformation was investigated on Au(111), Ag(111) and Cu(111) surfaces by performing spin-polarized density functional theory (DFT) calculations taking into account both van der Waals (vdW) interaction and on-site Coulomb repulsion. The deckchair conformation of the molecule favours intermolecular π–π-type interactions in a less densely packed monolayer than the saddle conformation. The activation barrier between the two stable magnetic states (high spin, S = 2 and intermediate spin, S = 1) of the molecule in vacuum disappears upon adsorption on the metal surfaces. The high-spin state of physisorbed FeTPP is stable on all adsorption sites. This result reveals that an external permanent element such as a STM tip or an additional molecule is needed to use FeTPP or similar molecules as model system for molecular spin switches.

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