Light-induced excited spin state trapping in a transition-metal complex: The hexa-1-propyltetrazole-iron (II) tetrafluoroborate spin-crossover system

Spin Transition Molecular Materials for displays and data recording

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-, oligoand 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.

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Spin state switching in iron coordination compounds

The discovery of a light-induced spin transition at cryogenic temperatures in a series of iron(II) spin-crossover compounds in 1984 has had an enormous impact on spin-crossover research. Apart from being an interesting photophysical phenomenon in its own right, it provided the means of studying the dynamics of the intersystem crossing process between the high-spin and the low-spin state in a series of compounds and over a large temperature range. It could thus be firmly established that intersystem crossing in spin-crossover compounds is a tunnelling process, with a limiting low-temperature lifetime below 50 K and a thermally activated region above 100 K. This review begins with an elucidation of the mechanism of the light-induced spin transition, followed by an in depth discussion of the chemical and physical factors, including cooperative effects, governing the lifetimes of the light-induced metastable states.

Light-induced spin crossover and the high-spin→low-spin relaxation

In der Ubergangsmetallchemie gibt es eine Klasse von Komplexverbindungen, bei denen eine Temperaturerniedrigung einen Wechsel im Spinzustand des Zentralatoms vom High-Spin- in den Low-Spin-Zustand bewirkt. Dabei andern sich die magnetischen und optischen Eigenschaften, uber die der thermische Spinubergang (auch Spincrossover genannt) sehr gut verfolgt werden kann. Dieses Phanomen tritt sowohl in flussiger Phase als auch im Festkorper auf. Eine herausragende Stellung nehmen Eisen(II) - Spincrossover - Verbindungen ein, in denen der Spinubergang im Festkorper auf sehr unterschiedliche Weise - graduell, abrupt, mit Hysterese oder stufenweise - verlaufen kann und mit Mosbauer- und optischer Spektroskopie, mit magnetischen Suszeptibilitats- und Warmekapazitatsmessungen sowie durch Kristallstrukturanalyse intensiv untersucht worden ist. Die kooperative Wechselwirkung zwischen den einzelnen Komplexmolekulen kann befriedigend durch elastische Eigenschaften und durch die Anderung von Gestalt und Volumen der Komplexmolekule beim Spinubergang erklart werden. Bei Untersuchungen an Eisen(II)-Spincrossover-Verbindungen konnte man beobachten, das sich der Low-Spin-Zustand mit grunem Licht in den High-Spin-Zustand umschalten last, der bei tiefen Temperaturen eine nahezu unendlich lange Lebensdauer haben kann (LIESST = Light-Induced Excited Spin State Trapping). Mit rotem Licht last sich der metastabile High-Spin- wieder in den Low-Spin-Zustand zuruckschalten. Der Mechanismus des LIESST-Effekts ist aufgeklart, die Zerfallskinetik im Detail untersucht und im Rahmen der Theorie strahlungsloser Ubergange verstanden. Anwendungen des LIESST-Effekts in der optischen Informationstechnik sind denkbar.

Thermisch und optisch schaltbare Eisen(II)‐Komplexe

Tetrazoles as ligands. Part IV. Iron(II) complexes of monofunctional tetrazole ligands, showing high-spin (p5T2g) ⇋ low-spin transitions

Transition metal(II) tetrafluoroborates react with 1-alkyltetrazoles to give complexes with six ligands per metal ion,viz.; ML6(BF4)2 with M2+ = Mn2+, Co2+, Ni2+, Cu2+ or Zn2+ and L =1-methyltetrazole (MTz), 1-ethyltetrazole (ETz) and 1-propyltetrazole (PTz). The complexes were identified and characterized by chemical analyses, i.r. and ligand field spectra. They are apparently mononuclear, containing monodentate ligands for which the Dq values are exceptionally high.

Tetrazoles as ligands, part III. Transition metal complexes of 1-alkyltetrazoles

Transition metal(II) ions and 5-cyanotetrazole (CNHT) form two types of compounds; type I with two 5-cyanotetrazolate (CNT) ions and an additional CNHT molecule and type II with only the two [CNT]− ions. Water molecules are invariable included in all compounds and are considered to be essential for the existence of the crystal structure. The complexes were identified and characterized by chemical analyses, i.r. and ligand field spectra. Some structural features have been predicted from these spectra and a polynuclear complex formation is apparent.

Peter L. Franke

Papers

Tetrazoles as ligands. Part IV. Iron(II) complexes of monofunctional tetrazole ligands, showing high-spin (p5T2g) ⇋ low-spin transitions

Tetrazoles as ligands, part III. Transition metal complexes of 1-alkyltetrazoles

Tetrazoles as ligands, part I. Transition metal(II) salts and complexes of 5-cyanotetrazole

Tetrazoles as ligands, Part II. The unexpected formation of transition metal(II) salts of 5-carbamyltetrazole