Search results for "Ligand field theory"
showing 9 items of 59 documents
Excited-state lifetimes of [Fe (bipy)3]2+ and [Fe(phen)3]2+
1990
Abstract In the low-spin [Fe(bipy)3]2+ (bipy = 2,2′,bipyridine) and [Fe(phen)3]2+ (phen = 1,10-phenanthroline) complexes an excited high-spin 5T2 ligand field state can be populated by irradiating into the 1MLCT absorption band at 530 nm. The lifetimes of this excited state at low temperatures are reported for [Fe(bipy)3]2+ doped into [Zn(bipy)3] (PF6)2 and [Zn(bipy)3] (BF4)2 and for [Fe(phen)3]2+ and [Fe(bipy)3]2+ embedded in the ion exchange polymer Nafion. For [Fe(bipy)3]2+ in [Zn(bipy)3](PF6)2 the observed lifetimes decrease from 1600 ns at 10 K to 14 ns at 125 K.
Three-Component Entanglements Consisting of Three Crescent-Shaped Bidentate Ligands Coordinated to an Octahedral Metal Centre
2007
3,3'-biisoquinoline ligands (biiq) L, bearing aromatic substituents on their 8 and 8' positions, have been used to generate interwoven systems consisting of three crescent-shaped ligands disposed around an octahedral metal centre. Mono-ligand complexes of the type [ReL(CO)3py]+ (py: pyridine) have also been prepared, leading to sterically non-hindering complexes in spite of the endotopic nature of the chelate used. The three-component entanglements have been prepared by using either FeII or RuII as gathering metal centre. The synthetic procedure is simple and efficient, affording fully characterised complexes as their PF6 or SbCl6 salts. X-ray crystallography clearly shows that the crescent…
Recent Advances of Spin Crossover Research
2004
Thermal spin transition (spin crossover), one of the most fascinating dynamic electronic structure phenomena occurring in coordination compounds of third row transition metal ions, mostly of iron(II), iron(III) and cobalt(II) with critical ligand field strengths competing with the spin pairing energy, has attracted increasing attention by many research groups. One of the reasons is the promising potential for practical applications. In this chapter we intend to cover essential recent work, primarily accomplished within the European research network on "Thermal and Optical Switching of Molecular Spin States (TOSS)". New spin crossover compounds and their thermal spin transition behaviour, al…
Light-Induced Excited Spin State Trapping in Iron(II) Complexes
1987
In the course of our studies on the thermally induced high spin (HS) ↔ low spin (LS) transition in iron(II) complexes /1/, \({\!^5{\text{T}}_2}_{\text{g}}\) ↔ \({\!^1{\text{A}}_1}_{\text{g}}\) in the approximation of Oh symmetry, we have observed in 1984 a new photophysical effect /2/: If, at sufficiently low temperature, the solid spin crossover complex is irradiated with green light into the \({\!^1{\text{A}}_1}\)→ \({\!^1{\text{T}}_1}\) ligand field absorption band, the thermodynamically stable LS state can be converted to the metastable HS state and trapped with practically infinite lifetime. We have called this unusual phenomenon “Light-Induced Excited Spin State Trapping (LIESST)”.
In Silico Molecular Engineering of Dysprosocenium-Based Complexes to Decouple Spin Energy Levels from Molecular Vibrations
2019
Molecular nanomagnets hold great promise for spintronics and quantum technologies, provided that their spin memory can be preserved above liquid-nitrogen temperatures. In the past few years, the magnetic hysteresis records observed for two related dysprosocenium-type complexes have highlighted the potential of molecular engineering to decouple vibrational excitations from spin states and thereby enhance magnetic memory. Herein, we study the spin-vibrational coupling in [(CpiPr5)Dy(Cp*)]+ (CpiPr5 = pentaisopropylcyclopentadienyl, Cp* = pentamethylcyclopentadienyl), which currently holds the hysteresis record (80 K), by means of a computationally affordable methodology that combines first-pri…
Towards Iron(II) Complexes with Octahedral Geometry: Synthesis, Structure and Photophysical Properties
2020
The control of ligand-field splitting in iron (II) complexes is critical to slow down the metal-to-ligand charge transfer (MLCT)-excited states deactivation pathways. The gap between the metal-centered states is maximal when the coordination sphere of the complex approaches an ideal octahedral geometry. Two new iron(II) complexes (C1 and C2), prepared from pyridylNHC and pyridylquinoline type ligands, respectively, have a near-perfect octahedral coordination of the metal. The photophysics of the complexes have been further investigated by means of ultrafast spectroscopy and TD-DFT modeling. For C1, it is shown that&mdash
Boosting Vis/NIR Charge-Transfer Absorptions of Iron(II) Complexes by N-Alkylation and N-Deprotonation in the Ligand Backbone.
2017
Reversing the 3MLCT / 3MC excited state order in iron(II) complexes is a challenging objective, yet would finally result in longsought luminescent transition metal complexes with an earthabundant central ion. One approach to achieve this goal is based on low-energy charge transfer absorptions in combination with a strong ligand field. Coordinating electron rich and electron poor tridentate oligopyridine ligands with large bite angles at iron(II) enables both low-energy MLCT absorption bands around 590 nm and a strong ligand field. Variations of the electron rich ligand by introducing longer alkyl substituents destabilizes the iron(II) complex towards ligand substitution reactions while hard…
Synthesis, crystal structure and properties of two acetazolamide (5-acetamido-1,3,4-thiadiazole-2-sulfonamide) complexes: bis(5-acetamidato- 1,3,4-th…
1992
Abstract The diverse coordination chemistry exhibited by acetazolamide (H2acm), a potent inhibitor of the carbonic anhydrase metalloenzyme, is highlighted in two new copper(II) complexes of this ligand: [Cu(Hacm)2(en)2] (I) and [Cu(Hacm)2(tn)2] (II). The synthesis, crystal structure and spectroscopic properties of both compounds are reported in this paper. The structures of both compounds consist of discrete units of [Cu(Hacm)2(en)2] (I) and [Cu(Hacm)2(tn)2] (II), respectively, interacting through van der Waals contacts and hydrogen bonds only. Hacm, however, binds differently in each compound. In both cases, the Cu(II) ions, lying on the symmetry centers, show an elongated octahedral geome…
Spin state switching in iron coordination compounds
2013
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 …