Now showing 1 - 4 of 4
  • Publication
    Room-temperature spin crossover and Langmuir-Blodgett film formation of an iron(II) triazole complex featuring a long alkyl chain substituent : the tail that wags the dog
    [FeII(C16dpt)2(NCS)2]·⅔H2O displays temperature-mediated spin crossover (SCO) with T½ = 290 K and the long alkyl chain substituent on the dipyridyltriazole ligand facilitates the formation of a stable Langmuir-Blodgett film at an air water interface.
    Scopus© Citations 67  520
  • Publication
    Organization of spin- and redox-labile metal centers into Langmuir and Langmuir-Blodgett films
    New sal2(trien) ligands that contain alkoxy substituents of various length in meta position of the salicyl entities were coordinated to electronically and magnetically active iron(III) and cobalt(III) centers. The electrochemical and spectroscopic properties of these amphiphilic complexes are virtually unaffected upon alteration of the alkoxy substituents, thus providing a system in which the physical behavior and the metal-centered chemical activity can be tailored independently. The amphiphilic character has been exploited for preparing Langmuir monolayers at the air-water interface and for constructing Langmuir-Blodgett films, hence allowing for hierarchical assembling of electronically and magnetically active systems. While Langmuir films were stable, transfer onto solid supports was limited, which restricted the magnetic analysis of the Langmuir-Blodgett assemblies.
      504Scopus© Citations 14
  • Publication
    A magnetic iron(III) switch with controlled and adjustable thermal response for solution processing
    Spin crossover requires cooperative behaviour of the metal centers in order to become useful for devices. While cooperativity is barely predictable in solids, we show here that solution processing and the covalent introduction of molecular recognition sites allows the spin crossover of iron(III) sal2trien complexes to be rationally tuned. A simple correlation between the number of molecular recognition sites and the spin crossover temperature enabled the fabrication of materials that are magnetically bistable at room temperature. The predictable behaviour relies on combining function (spin switching) and structure (supramolecular assembly) through covalent interactions in a single molecular building block.
    Scopus© Citations 35  454
  • Publication
    Towards Langmuir-Blodgett films of magnetically interesting materials: solution equilibria in amphiphilic iron(II) complexes of a triazole-containing ligand
    As a first step towards ambiphilic SCO systems where the hydrophobic part of the system is introduced by a non-coordinating anion (i.e. where no modification of the ligands to introduce hydrophobic substituents is required), [FeII(OH2)2(C16SO3)2] and [CoII(OH2)2(C16SO3)2] have been reacted with the triazole-containing ligands adpt and pldpt (C16SO¬3 = hexadecanesulfonate anion, adpt = 4-amino-3,5-bis(2-pyridyl)-1,2,4-triazole, pldpt = 4-pyrrolyl-3,5-bis(2-pyridyl)-1,2,4-triazole). In the solid state, HS complexes of the form [FeII(Rdpt)2(C16SO3)2] and [CoII(Rdpt)2(CH3OH)2](C16SO3)2 are observed, even when excess ligand is used (Rdpt = adpt or pldpt). In solution, the cobalt complexes remain in this form as evidenced by colour, Visible/NIR and IR spectroscopy. For the iron complexes, there is an equilibrium in solution between the neutral high-spin form of the complex [FeII(Rdpt)2(C16SO3)2] and the dicationic low-spin form [FeII(Rdpt)3](C16SO3)2. Polar solvents favour the dicationic form, while less polar solvents favour the neutral form (as evidenced by solution colour and solution IR spectroscopy). Visible/NIR spectroscopy and Evans’ method NMR spectroscopy show the equilibrium can be shifted towards the [FeII(Rdpt)3](C16SO3) form by adding additional ligand to the solution. The X-ray crystal structures of [FeII(adpt)2(C16SO3)2] and [CoII(adpt)2(CH3OH)2](C16SO3)2·1.33CH3OH are presented. [FeII(adpt)2(C16SO3)2] has a 2D bilayer structure with alternating layers of polar Fe(adpt)2 centres, and hydrophobic alkyl chains. The complex cations in [CoII(adpt)2(CH3OH)2](C16SO3)2·1.33CH3OH form 1-D columns in the solid state. The capacity of the amphiphilic complexes [FeII(pldpt)2(C16SO3)2] and [FeII(adpt)2(C16SO3)2] to self-assemble has been probed at the air-water interface using Langmuir techniques. The pertinent pressure-area isotherms reveal only a low tendency of the complexes to form films.
    Scopus© Citations 27  554