Bistable spin-crossover in a new series of [Fe(BPP-R)2]2+ (BPP = 2,6-bis(pyrazol-1-yl)pyridine; R = CN) complexes.

Spin-crossover (SCO) active transition metal complexes are a class of switchable molecular materials. Such complexes undergo hysteretic high-spin (HS) to low-spin (LS) transition, and vice versa, rendering them suitable for the development of molecule-based switching and memory elements. Therefore, the search for SCO complexes undergoing abrupt and hysteretic SCO, that is, bistable SCO, is actively carried out by the molecular magnetism community. In this study, we report the bistable SCO characteristics associated with a new series of iron(ii) complexes-[Fe(BPP-CN)2](X)2, X = BF4 (1a-d) or ClO4 (2)-belonging to the [Fe(BPP-R)2]2+ (BPP = 2,6-bis(pyrazol-1-yl)pyridine) family of complexes. Among the complexes, the lattice solvent-free complex 2 showed a stable and complete SCO (T1/2 = 241 K) with a thermal hysteresis width (ΔT) of 28 K-the widest ΔT reported so far for a [Fe(BPP-R)2](X)2 family of complexes, showing abrupt SCO. The reproducible and bistable SCO shown by the relatively simple [Fe(BPP-CN)2](X)2 series of molecular complexes is encouraging to pursue [Fe(BPP-R)2]2+ systems for the realization of technologically relevant SCO complexes.

Spin-crossover in iron(II)-phenylene ethynylene-2,6-di(pyrazol-1-yl) pyridine hybrids: toward switchable molecular wire-like architectures.

Luminescent oligo(p-phenylene ethynylene) (OPE) and spin-crossover (SCO) active Fe(II)-2,6-di(pyrazol-1-yl) pyridine (BPP) systems are prominent examples proposed to develop functional materials such as molecular wires/memories. A marriage between OPE and Fe(II)-BPP systems is a strategy to obtain supramolecular luminescent ligands capable of metal coordination useful to produce novel spin-switchable hybrids with synergistic coupling between spin-state of Fe(II) and a physical property associated with the OPE skeleton, for example, electronic conductivity or luminescence. To begin in this direction, two novel ditopic ligands, namely L1 and L2, featuring OPE-type backbone end-capped with metal coordinating BPP were designed and synthetized. The ligand L2 tailored with 2-ethylhexyloxy chains at the 2 and 5 positions of the OPE skeleton shows modulated optical properties and improved solubility in common organic solvents relative to the parent ligand L1. Solution phase complexation of L1 and L2 with Fe(BF4)2·6H2O resulted in the formation of insoluble materials of the composition [Fe(L1)] n (BF4)2n and [Fe(L2)] n (BF4)2n as inferred from elemental analyses. Complex [Fe(L1)] n (BF4)2n underwent thermal SCO centred at T 1/2 = 275 K as well as photoinduced low-spin to high-spin transition with the existence of the metastable high-spin state up to 52 K. On the other hand, complex [Fe(L2)] n (BF4)2n , tethered with 2-ethylhexyloxy groups, showed gradual and half-complete SCO with 50% of the Fe(II)-centres permanently blocked in the high-spin state due to intermolecular steric interactions. The small angle x-ray scattering (SAXS) pattern of the as-prepared solid complex [Fe(L1)] n (BF4)2n revealed the presence of nm-sized crystallites implying a possible methodology towards the template-free synthesis of functional-SCO nanostructures.

Bi-stable spin-crossover in charge-neutral [Fe(R-ptp)2] (ptp = 2-(1H-pyrazol-1-yl)-6-(1H-tetrazol-5-yl)pyridine) complexes.

Bi-stable charge-neutral iron(ii) spin-crossover (SCO) complexes are a class of switchable molecular materials proposed for molecule-based switching and memory applications. In this study, we report on the SCO behavior of a series of iron(ii) complexes composed of rationally designed 2-(1H-pyrazol-1-yl)-6-(1H-tetrazol-5-yl)pyridine (ptp) ligands. The powder forms of [Fe2+(R-ptp-)2]0 complexes tethered with less-bulky substituents-R = H (1), R = CH2OH (2), and R = COOCH3 (3; previously reported)-at the 4-position of the pyridine ring of the ptp skeleton showed abrupt and hysteretic SCO at or above room temperature (RT), whereas complex 5 featuring a bulky pyrene substituent showed incomplete and gradual SCO behavior. The role of intermolecular interactions, lattice solvent, and electronic nature of the chemical substituents (R) in tuning the SCO of the complexes is elucidated.

Spin-crossover in iron(ii)-Schiff base complexes.

The spin-crossover (SCO) phenomenon is one of the most prominent examples of bi-stability in molecular chemistry, and the SCO complexes are proposed for nanotechnological applications such as memory units, sensors, and displays. Since the discovery of the SCO phenomenon in tris(N,N-dialkyldithiocarbamato)iron(iii) complexes, numerous investigations have been made to obtain bi-stable SCO complexes undergoing spin-state switching at or around room temperature (RT). Valiant efforts have also been made to elucidate the structure-property relationship in SCO complexes to understand the factors-such as ligand-field strength, molecular geometry, and intermolecular interactions-governing the SCO. Schiff base ligands are an important class of nitrogen-rich chelating ligands used to prepare SCO complexes, because the Schiff base ligands are easy to synthesize and tailor with additional functionalities. Iron(ii)-Schiff base SCO complexes are a well-studied class of SCO active complexes due to the propensity of the complexes to undergo bi-stable SCO. In this context, this perspective attempts to elucidate the structure-SCO property relationships governing SCO in selected mono-, bi-, and multi-nuclear iron(ii)-Schiff base complexes.

Bi-stable spin-crossover characteristics of a highly distorted [Fe(1-BPP-COOC2H5)2](ClO4)2·CH3CN complex.

A highly distorted high spin Fe(ii)-complex, [Fe(1-BPP-COOC2H5)2](ClO4)2·CH3CN, with a trans-N(pyridine)-Fe-N(pyridine) angle (φ) of 158.83(17)° showed lattice solvent dependent bi-stable spin-state switching characteristics with T1/2 = ca. 233 K and a high thermal hysteresis width (ΔT) of 101 K, for the first cooling and heating cycle, unprecedented for the [Fe(BPP)2]2+ series of complexes; the results presented in this study are fundamentally important and have implications towards the realization of device architectures based on bi-stable SCO complexes.

Spin-state dependent conductance switching in single molecule-graphene junctions.

Spin-crossover (SCO) molecules are versatile magnetic switches with applications in molecular electronics and spintronics. Downscaling devices to the single-molecule level remains, however, a challenging task since the switching mechanism in bulk is mediated by cooperative intermolecular interactions. Here, we report on electron transport through individual Fe-SCO molecules coupled to few-layer graphene electrodes via π-π stacking. We observe a distinct bistability in the conductance of the molecule and a careful comparison with density functional theory (DFT) calculations allows to associate the bistability with a SCO-induced orbital reconfiguration of the molecule. We find long spin-state lifetimes that are caused by the specific coordination of the magnetic core and the absence of intermolecular interactions according to our calculations. In contrast with bulk samples, the SCO transition is not triggered by temperature but induced by small perturbations in the molecule at any temperature. We propose plausible mechanisms that could trigger the SCO at the single-molecule level.

A spin crossover (SCO) active graphene-iron(ii) complex hybrid material.

The advancement of molecular electronics and spintronics requires novel hybrid materials with synergistic magnetic and electrical properties. The non-covalent functionalization of highly conductive graphene with magnetically bistable spin crossover (SCO) complexes may yield such a multifunctional material. In this regard, a graphene-Fe(ii) SCO complex hybrid (Gr-SCO) has been prepared by non-covalently anchoring a pyrene decorated SCO complex with solution phase pre-exfoliated few-layer graphene sheets. SQUID magnetometry revealed the preservation of SCO in the Gr-SCO hybrid material exhibiting more gradual spin state switching characteristics than in the bulk molecular complex. This persistence of SCO of a molecular Fe(ii) complex upon anchoring on the graphene surface has consequences towards the realization of SCO based applications: in (i) reversible spin state dependent band gap tuning of graphene with an SCO complex analogous to chemical doping of graphene, and (ii) to probe the spin state dependence of electrical conductivity modulation by wiring the anchoring group (pyrene) tethered SCO complex between chemically robust few-layer graphene electrodes.

Highly luminescent charge-neutral europium(iii) and terbium(iii) complexes with tridentate nitrogen ligands.

We report on the synthesis of tridentate-nitrogen pyrazole-pyridine-tetrazole (L(1)H) and pyrazole-pyridine-triazole (L(2)H) ligands and their complexation with lanthanides (Ln = Gd(iii), Eu(iii) and Tb(iii)) resulting in stable, charge-neutral complexes Ln(L(1))3 and Ln(L(2))3, respectively. X-ray crystallographic analysis of the complexes with L(1) ligands revealed tricapped trigonal coordination geometry around the lanthanide ions. All complexes show bright photoluminescence (PL) in the solid state, indicating efficient sensitization of the lanthanide emission via the triplet states of the ligands. In particular, the terbium complexes show high PL quantum yields of 65 and 59% for L(1) and L(2), respectively. Lower PL efficiencies of the europium complexes (7.5 and 9%, respectively) are attributed to large energy gaps between the triplet states of the ligands and accepting levels of Eu(iii). The triplet state energy can be reduced by introducing an electron withdrawing (EW) group at the 4 position of the pyridine ring. Such substitution of L(1)H with a carboxylic ester (COOMe) EW group leads to a europium complex with increased PL quantum yield of 31%. A comparatively efficient PL of the complexes dissolved in ethanol indicates that the lanthanide ions are shielded against nonradiative deactivation via solvent molecules.