Vapochromic effect in switchable molecular-based spin crossover compounds.

Coordination complexes based on transition metal ions displaying [Ar]3d4-3d7 electronic configurations can undergo the likely most spectacular switchable phenomena found in molecular coordination chemistry, the well-known Spin Crossover (SCO). SCO phenomena is a detectable, reproducible and reversible switch that occurs between the high spin (HS) and low spin (LS) electronic states of the transition metal actuated by different stimuli (i.e. light, temperature, pressure, the presence of an analyte). Moreover, the occurrence of SCO phenomena causes different outputs, one of them being a colour change. Altogether, an analyte in gas form could be detected by naked eye once it has triggered the corresponding HS ↔ LS transition. This vapochromic effect could be used to detect volatile molecules using a low-cost technology, including harmful chemical substances, gases and/or volatile organic compounds (VOCs) that are present in our environment, in our home or at our workplace. The present review condenses all reported iron coordination compounds where the colour change induced by a given molecule in its gas form is coupled to a HS ↔ LS spin transition. Special emphasis has been made on describing the nature of the post-synthetic modification (PSM) taking place in the material upon the analyte uptake. In this case, three types of PSM can be distinguished: based on supramolecular contacts and/or leading to a coordinative or covalent bond. In the latter, a colour change not only indicates the switch of the spin state in the material but also the formation of a new compound with different properties. It is important to indicate that some of the SCO coordination compounds discussed in the current report have been part of other spin crossover reviews, that have gathered thermally induced SCO compounds and the influence of guest molecules on the SCO behaviour. However, in the majority of examples in these reviews, the change of colour upon the uptake of analytes is not associated with a spin transition at room temperature. In addition, the observed colour variations have been mainly discussed in terms of host-guest interactions, when they can also be induced by a PSM taking place in different sites of the molecule, like the Fe(II) coordination sphere or by chemically altering its inorganic and/or organic linkers. Therefore, we present here for the first time an exhaustive compilation of all systems in which the interaction between the coordination compounds and the vapour analytes leads to a colour change due to a spin transition in the metal centre at room temperature.

Playing with the weakest supramolecular interactions in a 3D crystalline hexakis[60]fullerene induces control over hydrogenation selectivity.

Weak forces can play an essential role in chemical reactions. Controlling such subtle forces in reorganization processes by applying thermal or chemical stimuli represents a novel synthetic strategy and one of the main targets in supramolecular chemistry. Actually, to separate the different supramolecular contributions to the stability of the 3D assemblies is still a major challenge. Therefore, a clear differentiation of these contributions would help in understanding the intrinsic nature as well as the chemical reactivity of supramolecular ensembles. In the present work, a controlled reorganization of an hexakis[60]fullerene-based molecular compound purely governed by the weakest van der Waals interactions known, i.e. the dihydrogen interaction - usually called sticky fingers - is illustrated. This pre-reorganization of the hexakis[60]fullerene under mild conditions allows a further selective hydrogenation of the crystalline material via hydrazine vapors exposure. This unique two-step transformation process is monitored by single-crystal to single-crystal diffraction (SCSC) which allows the direct observation of the molecular movements in the lattice and the subsequent solid-gas hydrogenation reaction.

Spin-state-dependent electrical conductivity in single-walled carbon nanotubes encapsulating spin-crossover molecules.

Spin crossover (SCO) molecules are promising nanoscale magnetic switches due to their ability to modify their spin state under several stimuli. However, SCO systems face several bottlenecks when downscaling into nanoscale spintronic devices: their instability at the nanoscale, their insulating character and the lack of control when positioning nanocrystals in nanodevices. Here we show the encapsulation of robust Fe-based SCO molecules within the 1D cavities of single-walled carbon nanotubes (SWCNT). We find that the SCO mechanism endures encapsulation and positioning of individual heterostructures in nanoscale transistors. The SCO switch in the guest molecules triggers a large conductance bistability through the host SWCNT. Moreover, the SCO transition shifts to higher temperatures and displays hysteresis cycles, and thus memory effect, not present in crystalline samples. Our results demonstrate how encapsulation in SWCNTs provides the backbone for the readout and positioning of SCO molecules into nanodevices, and can also help to tune their magnetic properties at the nanoscale.

Water Soluble Iron-Based Coordination Trimers as Synergistic Adjuvants for Pancreatic Cancer.

Pancreatic cancer is a usually fatal disease that needs innovative therapeutic approaches since the current treatments are poorly effective. In this study, based on cell lines, triazole-based coordination trimers made with soluble Fe(II) in an aqueous media were explored for the first time as adjuvant agents for the treatment of this condition. These coordination complexes were effective at relatively high concentrations and led to an increase in reactive oxygen species (ROS) in two pancreatic cancer cell lines, PANC-1 and BXPC-3, and this effect was accompanied by a significant reduction in cell viability in the presence of gemcitabine (GEM). Importantly, the tested compounds enhanced the effect of GEM, an approved drug for pancreatic cancer, through apoptosis induction and downregulation of the mTOR pathway. Although further evaluation in animal-based models of pancreatic cancer is needed, these results open novel avenues for exploring these iron-based materials in biomedicine in general and in pancreatic cancer treatment.

Covalent post-synthetic modification of switchable iron-based coordination polymers by volatile organic compounds: a versatile strategy for selective sensor development.

A covalent post-synthetic modification is applied in one of the most relevant polymers to obtain unprecedented switchable spin crossover (SCO) materials. We also demonstrate that this material can be used as a selective chemo-sensor for VOCs (particularly, formaldehyde) thanks to solid/vapor reactions occurring between the polymer and the corresponding vapor.

Tracking the Light-Induced Excited-State Dynamics and Structural Configurations of an Extraordinarily Long-Lived Metastable State at Room Temperature.

Time-resolved X-ray (Tr-XAS) and optical transient absorption (OTA) spectroscopy on the pico-microsecond timescale coupled with density functional theory calculations are applied to study the light-induced spin crossover processes of a Fe-based macrocyclic complex in solution. Tr-XAS analysis after light illumination shows the formation of a seven-coordinated high-spin quintet metastable state, which relaxes to a six-coordinated high-spin configuration before decaying to the ground state. Kinetic analysis of the macrocyclic complex reveals an unprecedented long-lived decay lifetime of approximately 42.6 µs. Comparative studies with a non-macrocyclic counterpart illustrate a significantly shortened approximately 568-fold decay lifetime of about 75 ns, and highlight the importance of the ligand arrangement in stabilizing the reactivity of the excited state. Lastly, OTA analysis shows the seven-coordinated high-spin state to be formed within approximately 6.2 ps. These findings provide a complete understanding of the spin crossover reaction and relaxation pathways of the macrocyclic complex, and reveal the importance of a flexible coordination environment for their rational design.

Divergent Adsorption-Dependent Luminescence of Amino-Functionalized Lanthanide Metal-Organic Frameworks for Highly Sensitive NO2 Sensors.

A novel gas sensing mechanism exploiting lanthanide luminescence modulation upon NO2 adsorption is demonstrated here. Two isostructural lanthanide-based metal-organic frameworks (MOFs) are used, including an amino group as the sensitive recognition center for NO2 molecules. The transfer of energy from the organic ligands to Ln is strongly dependent on the presence of NO2, resulting in an unprecedented photoluminescent sensing scheme. Thereby, NO2 exposition triggers either a reversible enhancement or a decrease in the luminescence intensity, depending on the lanthanide ion (Eu or Tb). Our experimental studies combined with density functional theory and complete active space self-consistent field calculations provide an understanding of the nature and effects of NO2 interactions within the MOFs and the signal transduction mechanism.

A Three-Dimensional Dynamic Supramolecular "Sticky Fingers" Organic Framework.

Engineering high-recognition host-guest materials is a burgeoning area in basic and applied research. The challenge of exploring novel porous materials with advanced functionalities prompted us to develop dynamic crystalline structures promoted by soft interactions. The first example of a pure molecular dynamic crystalline framework is demonstrated, which is held together by means of weak "sticky fingers" van der Waals interactions. The presented organic-fullerene-based material exhibits a non-porous dynamic crystalline structure capable of undergoing single-crystal-to-single-crystal reactions. Exposure to hydrazine vapors induces structural and chemical changes that manifest as toposelective hydrogenation of alternating rings on the surface of the [60]fullerene. Control experiments confirm that the same reaction does not occur when performed in solution. Easy-to-detect changes in the macroscopic properties of the sample suggest utility as molecular sensors or energy-storage materials.