Quantum chemical modeling of magnetically bistable metal coordination compounds. Synchronization of spin crossover, valence tautomerism and charge transfer induced spin transition mechanisms

2016 ◽  
Vol 45 (30) ◽  
pp. 12103-12113 ◽  
Author(s):  
V. I. Minkin ◽  
A. A. Starikova ◽  
A. G. Starikov

Heterometallic complexes of 1,10-phenanthroline-5,6-dione exhibiting unprecedented dynamic behaviour due to synchronized thermally induced intramolecular rearrangements were computationally studied.

2013 ◽  
Vol 9 ◽  
pp. 342-391 ◽  
Author(s):  
Philipp Gütlich ◽  
Ana B Gaspar ◽  
Yann Garcia

The article deals with coordination compounds of iron(II) that may exhibit thermally induced spin transition, known as spin crossover, depending on the nature of the coordinating ligand sphere. Spin transition in such compounds also occurs under pressure and irradiation with light. The spin states involved have different magnetic and optical properties suitable for their detection and characterization. Spin crossover compounds, though known for more than eight decades, have become most attractive in recent years and are extensively studied by chemists and physicists. The switching properties make such materials potential candidates for practical applications in thermal and pressure sensors as well as optical devices. The article begins with a brief description of the principle of molecular spin state switching using simple concepts of ligand field theory. Conditions to be fulfilled in order to observe spin crossover will be explained and general remarks regarding the chemical nature that is important for the occurrence of spin crossover will be made. A subsequent section describes the molecular consequences of spin crossover and the variety of physical techniques usually applied for their characterization. The effects of light irradiation (LIESST) and application of pressure are subjects of two separate sections. The major part of this account concentrates on selected spin crossover compounds of iron(II), with particular emphasis on the chemical and physical influences on the spin crossover behavior. The vast variety of compounds exhibiting this fascinating switching phenomenon encompasses mono-, oligo- and polynuclear iron(II) complexes and cages, polymeric 1D, 2D and 3D systems, nanomaterials, and polyfunctional materials that combine spin crossover with another physical or chemical property.


2017 ◽  
Vol 41 (14) ◽  
pp. 6497-6503 ◽  
Author(s):  
A. A. Starikova ◽  
V. I. Minkin

A new series of transition metal coordination compounds capable of manifesting the properties of logical elements of quantum computers has been computationally designed using the DFT UB3LYP*/6-311++G(d,p) calculations.


2019 ◽  
Author(s):  
Tim Stauch ◽  
Romit Chakraborty ◽  
Martin Head-Gordon

Spin state switching on external stimuli is a phenomenon with wide applicability ranging from molecular electronics to gas activation in nanoporous frameworks. Here we model spin crossover as a function of hydrostatic pressure in octahedrally coordinated transition metal centers by applying a field of effective nuclear forces that compress the molecule towards its centroid. For spin crossover in first-row transition metals coordinated by hydrogen, nitrogen, and carbon monoxide, we find the pressure required for spin transition to be a function of ligand position in the spectrochemical sequence. While pressures on the order of 1 GPa are required to flip spins in homogeneously ligated octahedral sites, we demonstrate a five-fold decrease in spin transition pressure for the archetypal strong field ligand carbon monoxide in octahedrally coordinated Fe<sup>2+</sup> in [Fe(II)(NH<sub>3</sub>)<sub>5</sub>CO]<sup>2+</sup>.


Author(s):  
Pradip Chakraborty ◽  
Mouhamadou Sy ◽  
Houcem Fourati ◽  
Maria Teresa Delgado Pérez ◽  
Mousumi Dutta ◽  
...  

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...


ChemPhysChem ◽  
2019 ◽  
Vol 20 (21) ◽  
pp. 2742-2747 ◽  
Author(s):  
Tim Stauch ◽  
Romit Chakraborty ◽  
Martin Head‐Gordon

2015 ◽  
Vol 54 (16) ◽  
pp. 7906-7914 ◽  
Author(s):  
Francisco Javier Valverde-Muñoz ◽  
Ana B. Gaspar ◽  
Sergii I. Shylin ◽  
Vadim Ksenofontov ◽  
José A. Real

2016 ◽  
Vol 40 (11) ◽  
pp. 9012-9016 ◽  
Author(s):  
Il'ya A. Gural'skiy ◽  
Sergii I. Shylin ◽  
Bohdan O. Golub ◽  
Vadim Ksenofontov ◽  
Igor O. Fritsky ◽  
...  

Thermally induced spin transition at 370 K has been observed in a Hofmann-clathrate-like metal–organic framework.


Polyhedron ◽  
2005 ◽  
Vol 24 (16-17) ◽  
pp. 2909-2912 ◽  
Author(s):  
Akio Nakamoto ◽  
Norimichi Kojima ◽  
Liu XiaoJun ◽  
Yutaka Moritomo ◽  
Arao Nakamura

Crystals ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 843
Author(s):  
Olga G. Shakirova ◽  
Ludmila G. Lavrenova

We review here new advances in the synthesis and investigation of iron(II) coordination compounds with tris(pyrazol-1-yl)methane and its derivatives as ligands. The complexes demonstrate thermally induced spin crossover accompanied by thermochromism. Factors that influence the nature and temperature of the spin crossover are discussed.


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