Spin crossover of a Fe(II) mononuclear complex induced by intermolecular factors involving chloride and solvent ordering.

Two new salts of a mononuclear tripodal Fe(II) complex were prepared, using ClO4- and Cl-. The ClO4- sample (1) remained HS at low temperatures, similar to the previously reported BF4- analogue. Crystallising with the Cl- anion (2) led to a markedly different crystal packing arrangement, and engendered SCO activity. This has been correlated to the lower crystal packing density in 2 and the coordination complex conformational differences arising due to the packing motifs of 1 and 2. Further, solvent ordering effects have been proposed to facilitate spin transition behaviour in 2.

Spin Crossover Induced by Changing the Identity of the Secondary Metal Ion from PdII to NiII in a Face-Centered FeII 8 MII 6 Cubic Cage.

Discrete spin crossover (SCO) heteronuclear cages are a rare class of materials which have potential use in next-generation molecular transport and catalysis. Previous investigations of cubic cage [Fe8 Pd6 L8 ]28+ constructed using semi-rigid metalloligands, found that FeII centers of the cage did not undergo spin transition. In this work, substitution of the secondary metal center at the face of the cage resulted in SCO behavior, evidenced by magnetic susceptibility, Mössbauer spectroscopy and single crystal X-ray diffraction. Structural comparisons of these two cages shed light on the possible interplay of inter- and intramolecular interactions associated with SCO in the NiII analogue, 1 ([Fe8 Ni6 L8 (CH3 CN)12 ]28+ ). The distorted octahedral coordination environment, as well as the occupation of the CH3 CN in the NiII axial positions of 1, prevented close packing of cages observed in the PdII analogue. This led to offset, distant packing arrangements whereby important areas within the cage underwent dramatic structural changes with the exhibition of SCO.

A complementary characterisation technique for spin crossover materials; the application of X-ray photoelectron spectroscopy for future device applications.

Spin crossover (SCO) materials have long been studied for their inherent electronic switchability, which has been well investigated for potential application in electronic and switching devices. As the technologies for the fabrication of thin films and monolayers continue to develop at an exceedingly rapid pace, an emerging challenge for the SCO community has become the characterisation of spin transitions in the surface layers of a material, as well as understanding the origins of discrepancies observed between SCO in thin films and that of the bulk material. For the manufacture of such devices to become a reality, it is crucial to understand how spin crossover is affected by interactions with the substrate material and within thin films. As such, detailed analysis of the surface layers without interference from the substrate material emerged as a critical area of characterisation for future developments in SCO devices. In this regard, X-ray Photoelectron Spectroscopy (XPS) has emerged as a complementary technique for the analysis of SCO in the surface layers of a material, becoming an essential part of a multi-technique protocol that is driving advances in the field. Here we describe the complementary application of XPS to a variety of SCO materials, review major developments and provide illustrative examples of innovations made through surface analysis with XPS.

Supramolecular Modulation of Spin Crossover in an Fe(II) Dinuclear Triple Helicate.

A spin-crossover (SCO) active dinuclear Fe(II) triple helicate of the form [Fe2L3]4+ was combined with additional supramolecular components in order to manipulate the interhelical separation and steric congestion and to study the magneto-structural effects on the ensuing composite materials. A more separated array of SCO units produced more extensive spin-transitions, while a tightly arranged lattice environment stabilized the low-spin state. This study highlights the important interplay between crystal packing, intermolecualr interactions, and the magentic behavior of SCO materials.

A large dinuclear Fe(ii) triple helicate demonstrating a two-step spin crossover.

Reported herein, the synthesis as well as the structural and magnetic characterisation of the largest reported dinuclear Fe(ii) triple helicate system to exhibit spin crossover-and also a rare example of a 273° helical twist using aromatic spacers-is presented, with exploration of the two-step spin-transition observed.

A Rare Example of a Complete, Incomplete, and Non-Occurring Spin Transition in a [Fe2L3]X4 Series Driven by a Combination of Solvent-and Halide-Anion-Mediated Steric Factors.

A trend between the degree of steric congestion of the Fe(II) coordination environment and the extent of spin transition (percentage completeness) has been observed in a series of halide salts of a dinuclear triple helicate architecture with the general form [Fe2L3]X4 (where X = Cl- for 1, Br- for 2, and (I-)3/I3- for 3, and L is (1E,1'E)-N,N'-(oxybis(4,1-phenylene))bis(1-(1H-imidazol-4-yl)methanimine). Crystal packing densities of adjacent helicates were found to decrease with increasing anion size. Greater steric congestion by neighboring helicates favored the [HS-HS] state of the dinuclear triple helicate architecture. As a result, the highly crowded Cl- salt (1) did not undergo spin-crossover (SCO), the more congested Br- salt (2) underwent an incomplete solvent-dependent transition, and the least crowded (I-)3/I3- analogue (3) exhibited a full SCO from the [HS-HS] ↔ [LS-LS] state. Furthermore, an interesting two-step transition was observed in the Br- salt, exhibiting a 28 K thermal hysteresis in the higher temperature step, the largest thermal hysteresis reported to date for a Fe(II) dinuclear triple helicate system. Variable-temperature single-crystal X-ray diffraction (SCXRD) analysis of 2 demonstrated that this two-step profile was found to be the result of crystallographic parameters evolving in a two-step manner with temperature, rather than a crystallographic phase change.

A mixed-spin spin-crossover thiozolylimine [Fe4L6]8+ cage.

The self-assembly of a mixed-spin [Fe4L6]8+ tetrahedral cage is reported. The cage undergoes temperature induced spin-crossover with a 29 K hystereisis. Variable temperature X-ray photoelectron spectroscopy (VT-XPS), combined with SQUID data, allowed differentiation between the surface and bulk magnetic properties.

Investigation of the High-Temperature Spin-Transition of a Mononuclear Iron(II) Complex Using X-ray Photoelectron Spectroscopy.

This study presents a new mononuclear complex (1) of the form [FeL](BF4)2, incorporating the thiazolylimine donor moiety, which was found to exhibit a high-temperature spin-transition. The effect of scan rate was investigated, with magnetic susceptibility being measured at 4, 2, and 1 K min-1. The magnetic susceptibility results were confirmed by variable temperature X-ray photoelectron spectroscopy (XPS) (100, 270, 400, and 500 K) and single crystal X-ray diffraction (150 and 400 K) experiments. A rare example of a high-temperature (400 K) single crystal structure of 1 has been reported. The high-spin fraction was calculated indirectly from XPS data, presenting a method for analyzing the spin-state in the surface layers of spin-crossover materials.

Direct monitoring of spin transitions in a dinuclear triple-stranded helicate iron(ii) complex through X-ray photoelectron spectroscopy.

A dinuclear helical iron(ii) complex of a new ditopic thiazolylimine ligand (L) has been synthesised via supramolecular assembly. The resulting dinuclear helical cylinder [Fe2L3]·4BF4 was investigated by variable temperature X-ray crystallography, ESI high resolution mass spectrometry, CHN analysis, FT-IR and UV-Vis spectroscopy. The nature of the spin transition was investigated by magnetic susceptibility measurements, and confirmed by VT-SCXRD and X-ray photoelectron spectroscopy. [Fe2L3]·4BF4 displays a complete spin transition with a gradual-abrupt character at T1/2 = 348 K and represents a new example of a dinuclear iron(ii) complex exhibiting a spin transition at high temperature. Both VT-SCXRD and XPS measurements show excellent correlation with the magnetic susceptibility experiments, demonstrating the power of XPS not just to confirm, but also to clearly follow the spin-state transition in Fe(ii) SCO complexes.

Ultrasensitive Colorimetric and Ratiometric Detection of Cu2+: Acid-Base Properties, Complexation, and Binding Studies.

Herein, we report the synthesis and characterization of a chemosensor, 5-(diethylamino)-2-(2,3-dihydro-1H-perimidin-2-yl)phenol (HL), synthesized from a condensation between 4-(diethylamino)salicylaldehyde and 1,8-diaminonaphthalene. Upon investigation of the sensing properties of HL, it was found that this sensor may be employed for simple yet efficient detection of Cu2+ in aqueous methanol solutions. The selective and ratiometric response to Cu2+ yielded an outstandingly low limit of detection of 3.7 nM by spectrophotometry and is also useful as a naked-eye sensor from 2.5 µM. The system was studied by spectrophotometric pH titrations to determine Cu2+ binding constants and complex speciation. Binding of Cu2+ to HL occurs in 1:1 stoichiometry, in good agreement with high-resolution electrospray ionization mass spectrometry (ESI-HRMS) results, Cu2+ titrations, and Job's plot experiments, while the coordination geometry was tentatively assigned as square pyramidal by spectroscopic studies.

Synthesis and characterisation of new tripodal lanthanide complexes and investigation of their optical and magnetic properties.

This paper presents the synthesis of a tripodal ligand (H3L) via the Schiff base condensation of N,N-diethylsalicylaldehyde and tris(2-aminoethyl)amine. The neutral complexes of type [EuL], [GdL] and [DyL] were synthesized and characterized by FT-IR, SEM-EDS, PXRD, single crystal X-ray diffraction, CHN analysis and high resolution ESI-MS. X-ray crystallographic studies demonstrated that the heptadentate ligand incorporating a cavity pre-organized by hydrogen bonding binds the Ln(iii) ions to yield a face capped octahedral coordination geometry with three-fold symmetry. Photoluminescence studies show a typical Ln(iii) absorption character for the three complexes, with [EuL] demonstrating considerably stronger lanthanide-based luminescence peaks, and a Eu(iii) centered luminescence lifetime of 0.144 ± 0.01 ms. Temperature/field-dependent DC and temperature/frequency-dependent AC magnetic measurements carried out for the Dy(iii) complex indicated obvious magnetic anisotropy and suggested slow relaxation behaviour with considerable quantum tunnelling of the magnetization contribution.

Spin-State Patterning in an Iron(II) Tripodal Spin-Crossover Complex.

A mononuclear iron(II) complex that displays a gradual two-step spin-crossover (SCO) transition is reported. The intermediate plateau (IP) occurs between HS0.40LS0.60 and HS0.30LS0.70 (HS = high spin; LS = low spin) ratios over the region of ca. 190-170 K. A phase change occurs at the IP, breaking the symmetry, resulting in six independent SCO sites compared to one at the 100% HS and LS plateau regions, respectively. Variable-temperature X-ray photoelectron spectroscopy shows that the SCO behavior is completely reversible among the HS, IP, and LS regions. The results both confirm and extend the related results for the above system described by Halcrow et al. (Kulmaczewski R.; Cespedes O.; Halcrow M. A.Gradual Thermal Spin-Crossover Mediated By a Reentrant Z' = 1 → Z' = 6 → Z' = 1 Phase Transition, Inorg. Chem. 2017, 56, 3144-3148) in a recent report.