This article reviews the most relevant chemical and structural aspects that influence the spin-crossover phenomenon (SCO). Special attention is focussed on the recent development of SCO coordination polymers. The different approaches currently being explored in order to achieve multifunctionality in SCO materials are discussed.

Thermal, pressure and light switchable spin-crossover materials

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 observation of spin crossover with thermal hysteresis loops of more than a few Kelvin remains relatively uncommon and unpredictable, so is a relatively underdeveloped, but important, area of spin crossover, particularly for memory applications. Lessons learnt regarding the origins, and the practicalities of the proper study and reporting, of thermal hysteresis loops are considered and explained, from a synthetic chemists perspective, after a general introduction to the field of spin crossover.

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Spin crossover with thermal hysteresis: practicalities and lessons learnt.

Although the oxidation of water is efficiently catalysed by the oxygen-evolving complex in photosystem II (refs 1 and 2), it remains one of the main bottlenecks when aiming for synthetic chemical fuel production powered by sunlight or electricity. Consequently, the development of active and stable water oxidation catalysts is crucial, with heterogeneous systems considered more suitable for practical use and their homogeneous counterparts more suitable for targeted, molecular-level design guided by mechanistic understanding. Research into the mechanism of water oxidation has resulted in a range of synthetic molecular catalysts, yet there remains much interest in systems that use abundant, inexpensive and environmentally benign metals such as iron (the most abundant transition metal in the Earth's crust and found in natural and synthetic oxidation catalysts). Water oxidation catalysts based on mononuclear iron complexes have been explored, but they often deactivate rapidly and exhibit relatively low activities. Here we report a pentanuclear iron complex that efficiently and robustly catalyses water oxidation with a turnover frequency of 1,900 per second, which is about three orders of magnitude larger than that of other iron-based catalysts. Electrochemical analysis confirms the redox flexibility of the system, characterized by six different oxidation states between Fe(II)5 and Fe(III)5; the Fe(III)5 state is active for oxidizing water. Quantum chemistry calculations indicate that the presence of adjacent active sites facilitates O-O bond formation with a reaction barrier of less than ten kilocalories per mole. Although the need for a high overpotential and the inability to operate in water-rich solutions limit the practicality of the present system, our findings clearly indicate that efficient water oxidation catalysts based on iron complexes can be created by ensuring that the system has redox flexibility and contains adjacent water-activation sites.

A pentanuclear iron catalyst designed for water oxidation

Multifunctionality in spin crossover materials

Direct two-step spin-crossover through [HS–HS]⋯[LS–LS] at the plateau in dinuclear diiron(II) complex [{Fe(NCBH3)(4phpy)}2(μ-bpypz)2]

Two series of pyrazolato bridged dinuclear NCS and NCBH3 diiron(II) complexes with various types of 3- or 4-substituted pyridines, [{Fe(NCS or NCBH3)(X-py)}2(mu-bpypz)2], were prepared and their variable-temperature magnetic susceptibilities were measured. There were found linear correlations of the spin-crossover temperatures Tc not only between the NCS and NCBH3 complexes with the corresponding substituted pyridines, but also between the Tc and the Hammett constants, supporting the electronic substituent effect of the coordinated pyridine rather than a steric effect. The ligand field and the interelectronic repulsion parameters together with the thermodynamic data and/or cooperativity factor were discussed in relation with their spin-crossover behavior.

Substituent effect of the coordinated pyridine in a series of pyrazolato bridged dinuclear diiron(II) complexes on the spin-crossover behavior

An [Fe(II) (3)O](4+) core wrapped by two [Fe(II)L(3)](-) units.

An [FeII3O]4+ Core Wrapped by Two [FeIIL3]− Units

A steep one-step [HS-HS] to [LS-LS] spin transition in a 4,4'-bipyridine linked one-dimensional coordination polymer constructed from a pyrazolato bridged Fe(II) dimer.

Ko Yoneda

Papers

Direct two-step spin-crossover through [HS–HS]⋯[LS–LS] at the plateau in dinuclear diiron(II) complex [{Fe(NCBH3)(4phpy)}2(μ-bpypz)2]

Substituent effect of the coordinated pyridine in a series of pyrazolato bridged dinuclear diiron(II) complexes on the spin-crossover behavior

An [Fe(II) (3)O](4+) core wrapped by two [Fe(II)L(3)](-) units.

An [FeII3O]4+ Core Wrapped by Two [FeIIL3]− Units

A steep one-step [HS-HS] to [LS-LS] spin transition in a 4,4'-bipyridine linked one-dimensional coordination polymer constructed from a pyrazolato bridged Fe(II) dimer.