Translocation and Confinement of Tetraamines in Adaptable Microporous Cavities.

Metal-Organic Frameworks can be grafted with amines by coordination to metal vacancies to create amine-appended solid adsorbents, which are being considered as an alternative to using aqueous amine solutions for CO2 capture. In this study, we propose an alternative mechanism that does not rely on the use of neutral metal vacancies as binding sites but is enabled by the structural adaptability of heterobimetallic Ti2Ca2 clusters. The combination of hard (Ti4+) and soft (Ca2+) metal centers in the inorganic nodes of the framework enables MUV-10 to adapt its pore windows to the presence of triethylenetetramine molecules. This dynamic cluster response facilitates the translocation and binding of tetraamine inside the microporous cavities to enable the formation of bis-coordinate adducts that are stable in water. The extension of this grafting concept from MUV-10 to larger cavities not restrictive to CO2 diffusion will complement other strategies available for the design of molecular sorbents for decarbonization applications.

Isoreticular Expansion and Linker-Enabled Control of Interpenetration in Titanium-Organic Frameworks.

Titanium-organic frameworks offer distinctive opportunities in the realm of metal-organic frameworks (MOFs) due to the integration of intrinsic photoactivity or redox versatility in porous architectures with ultrahigh stability. Unfortunately, the high polarizing power of Ti4+ cations makes them prone to hydrolysis, thus preventing the systematic design of these types of frameworks. We illustrate the use of heterobimetallic cluster Ti2Ca2 as a persistent building unit compatible with the isoreticular design of titanium frameworks. The MUV-12(X) and MUV-12(Y) series can be all synthesized as single crystals by using linkers of varying functionalization and size for the formation of the nets with tailorable porosity and degree of interpenetration. Following the generalization of this approach, we also gain rational control over interpenetration in these nets by designing linkers with varying degrees of steric hindrance to eliminate stacking interactions and access the highest gravimetric surface area reported for titanium(IV) MOFs (3000 m2 g-1).

Metal Node Control of Brønsted Acidity in Heterobimetallic Titanium-Organic Frameworks.

Compared to indirect framework modification, synthetic control of cluster composition can be used to gain direct access to catalytic activities exclusive of specific metal combinations. We demonstrate this concept by testing the aminolysis of epoxides with a family of isostructural mesoporous frameworks featuring five combinations of homometallic and heterobimetallic metal-oxo trimers (Fe3, Ti3, TiFe2, TiCo2, and TiNi2). Only TiFe2 nodes display activities comparable to benchmark catalysts based on grafting of strong acids, which here originate from the combination of Lewis Ti4+ and Brønsted Fe3+-OH acid sites. The applicability of MUV-101(Fe) to the synthesis of ß-amino alcohols is demonstrated with a scope that also includes the gram scale synthesis of propranolol, a natural ß-blocker listed as an essential medicine by the World Health Organization, with excellent yield and selectivity.

Hybrid Heterostructures of a Spin Crossover Coordination Polymer on MoS2 : Elucidating the Role of the 2D Substrate.

Controlling the deposition of spin-crossover (SCO) materials constitutes a crucial step for the integration of these bistable molecular systems in electronic devices. Moreover, the influence of functional surfaces, such as 2D materials, can be determinant on the properties of the deposited SCO film. In this work, ultrathin films of the SCO Hofmann-type coordination polymer [Fe(py)2 {Pt(CN)4 }] (py = pyridine) onto monolayers of 1T and 2H MoS2 polytypes are grown. The resulting hybrid heterostructures are characterized by GIXRD, XAS, XPS, and EXAFS to get information on the structure and the specific interactions generated at the interface, as well as on the spin transition. The use of a layer-by-layer results in SCO/2D heterostructures, with crystalline and well-oriented [Fe(py)2 {Pt(CN)4 }]. Unlike with conventional Au or SiO2 substrates, no intermediate self-assembled monolayer is required, thanks to the surface S atoms. Furthermore, it is observed that the higher presence of Fe3+ in the 2H heterostructures hinders an effective spin transition for [Fe(py)2 {Pt(CN)4 }] films thinner than 8 nm. Remarkably, when using 1T MoS2 , this transition is preserved in films as thin as 4 nm, due to the reducing character of this metallic substrate. These results highlight the active role that 2D materials play as substrates in hybrid molecular/2D heterostructures.

Tetrazine Linkers as Plug-and-Play Tags for General Metal-Organic Framework Functionalization and C60 Conjugation.

The value of covalent post-synthetic modification in expanding the chemistry and pore versatility of reticular solids is well documented. Here we use mesoporous crystals of the metal-organic framework (MOF) UiO-68-TZDC to demonstrate the value of tetrazine connectors for all-purpose inverse electron-demand Diels-Alder ligation chemistry. Our results suggest a positive effect of tetrazine reticulation over its reactivity for quantitative one-step functionalization with a broad scope of alkene or alkyne dienophiles into pyridazine and dihydropyridazine frameworks. This permits generating multiple pore environments with diverse chemical functionalities and the expected accessible porosities, that is also extended to the synthesis of crystalline fulleretic materials by covalent conjugation of fullerene molecules.

Effect of Linker Distribution in the Photocatalytic Activity of Multivariate Mesoporous Crystals.

The use of Metal-Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single-component phases or even access new functions. This approach is particularly relevant for Zr6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials are isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use high-throughput methodologies to optimize the synthesis of single crystals of UiO-68 and UiO-68-TZDC, a photoactive analogue based on a tetrazine dicarboxylic derivative. The analysis of the single linker phases reveals the necessity of combining both linkers to produce multivariate frameworks that combine efficient light sensitization, chemical stability, and porosity, all relevant to photocatalysis. We use solvent-assisted linker exchange reactions to produce a family of UiO-68-TZDC% binary frameworks, which respect the integrity and morphology of the original crystals. Our results suggest that the concentration of TZDC in solution and the reaction time control the distribution of this linker in the sibling crystals for a uniform mixture or the formation of core-shell domains. We also demonstrate how the possibility of generating an asymmetric distribution of both linkers has a negligible effect on the electronic structure and optical band gap of the solids but controls their performance for drastic changes in the photocatalytic activity toward proton or methyl viologen reduction.

Electrical conductivity and magnetic bistability in metal-organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale.

Materials scientists are currently shifting from purely inorganic, organic and silicon-based materials towards hybrid organic-inorganic materials to develop increasingly complex and powerful electronic devices. In this context, it is undeniable that conductive metal-organic frameworks (MOFs) and bistable coordination polymers (CPs) are carving a niche for themselves in the electronics world. The tunability and processability of these materials alongside the combination of electrical conductivity with porosity or spin transition offers unprecedented technological opportunities for their integration into functional devices. This review aims to summarise the chemical strategies that have guided the design of this type of materials and the identified opportunities for further development. We also examine the strategies to process them as thin films and stress the importance of analysing the effects of nanostructuration on their physical properties that might be crucial for device performance. Finally, we showcase relevant examples of functional devices that have received increasing attention from researchers and highlight the opportunities available for more sophisticated applications that could take full advantage of the combination of electrical conductivity and magnetic bistability.

Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium-Organic Frameworks.

We introduce the first example of isoreticular titanium-organic frameworks, MUV-10 and MUV-12, to show how the different affinity of hard Ti(IV) and soft Ca(II) metal sites can be used to direct selective grafting of amines. This enables the combination of Lewis acid titanium centers and available -NH2 sites in two sizeable pores for cooperative cycloaddition of CO2 to epoxides at room temperature and atmospheric pressure. The selective grafting of molecules to heterometallic clusters adds up to the pool of methodologies available for controlling the positioning and distribution of chemical functions in precise positions of the framework required for definitive control of pore chemistry.

Heterometallic Titanium-Organic Frameworks by Metal-Induced Dynamic Topological Transformations.

Reticular chemistry has boosted the design of thousands of metal and covalent organic frameworks for unlimited chemical compositions, structures, and sizable porosities. The ability to generate porous materials at will on the basis of geometrical design concepts is responsible for the rapid growth of the field and the increasing number of applications derived. Despite their promising features, the synthesis of targeted homo- and heterometallic titanium-organic frameworks amenable to these principles is relentlessly limited by the high reactivity of this metal in solution that impedes the controlled assembly of titanium molecular clusters. We describe an unprecedented methodology for the synthesis of heterometallic titanium frameworks by metal-exchange reactions of MOF crystals at temperatures below those conventionally used in solvothermal synthesis. The combination of hard (titanium) and soft (calcium) metals in the heterometallic nodes of MUV-10(Ca) enables controlled metal exchange in soft positions for the generation of heterometallic secondary building units (SBUs) with variable nuclearity, controlled by the metal incorporated. The structural information encoded in the newly formed SBUs drives an MOF-to-MOF conversion into bipartite nets compatible with the connectivity of the organic linker originally present in the crystal. Our simulations show that this transformation has a thermodynamic origin and is controlled by the terminations of the (111) surfaces of the crystal. The reaction of MUV-10(Ca) with first-row transition metals permits the production of crystals of MUV-101(Fe,Co,Ni,Zn) and MUV-102(Cu), heterometallic titanium MOFs isostructural with archetypical solids such as MIL-100 and HKUST. In comparison to de novo synthesis, this metal-induced topological transformation provides control over the formation of hierarchical micro-/mesopore structures at different reaction times and enables the formation of heterometallic titanium MOFs not accessible under solvothermal conditions at high temperature, thus opening the door for the isolation of additional titanium heterometallic phases not linked exclusively to trimesate linkers.

Reinforced Room-Temperature Spin Filtering in Chiral Paramagnetic Metallopeptides.

Chirality-induced spin selectivity (CISS), whereby helical molecules polarize the spin of electrical current, is an intriguing effect with potential applications in nanospintronics. In this nascent field, the study of the CISS effect using paramagnetic chiral molecules, which could introduce another degree of freedom in controlling the spin transport, remains so far unexplored. To address this challenge, herein we propose the use of self-assembled monolayers (SAMs) of helical lanthanide-binding peptides. To elucidate the effect of the paramagnetic nuclei, monolayers of the peptide coordinating paramagnetic or diamagnetic ions are prepared. By means of spin-dependent electrochemistry, the CISS effect is demonstrated by cyclic voltammetry and electrochemical impedance measurements for both samples. Additionally, an implementation of the standard liquid-metal drop electron transport setup has been carried out, and this process helped to demonstrate the peptides' suitability for solid-state devices. Remarkably, the inclusion of a paramagnetic center in the peptide increases the spin polarization as was independently proved by different techniques. These findings permit the inclusion of magnetic biomolecules in the CISS field and pave the way to their implementation in a new generation of (bio)spintronic nanodevices.

WS2 /MoS2 Heterostructures through Thermal Treatment of MoS2 Layers Electrostatically Functionalized with W3 S4 Molecular Clusters.

The preparation of 2D stacked layers combining flakes of different nature gives rise to countless numbers of heterostructures where new band alignments, defined at the interfaces, control the electronic properties of the system. Among the large family of 2D/2D heterostructures, the one formed by the combination of the most common semiconducting transition metal dichalcogenides, WS2 /MoS2 , has awakened great interest owing to its photovoltaic and photoelectrochemical properties. Solution as well as dry physical methods have been developed to optimize the synthesis of these heterostructures. Here, a suspension of negatively charged MoS2 flakes is mixed with a methanolic solution of a cationic W3 S4 -core cluster, giving rise to a homogeneous distribution of the clusters over the layers. In a second step, a calcination of this molecular/2D heterostructure under N2 leads to the formation of clean WS2 /MoS2 heterostructures, where the photoluminescence of both counterparts is quenched, proving an efficient interlayer coupling. Thus, this chemical method combines the advantages of a solution approach (simple, scalable, and low-cost) with the good quality interfaces reached by using more complicated traditional physical methods.

Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal-Organic Framework.

Metal-organic frameworks can be used as porous templates to exert control over polymerization reactions. Shown here are the possibilities offered by these crystalline, porous nanoreactors to capture highly-reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework the polymerization of pyrrole is restricted, capturing the formation of terpyrrole cationic intermediates. Single-crystal X-ray diffraction is used to provide definite information on the supramolecular interactions that induce the formation and stabilization of a conductive array of cationic complexes.

Origin of the Chemiresistive Response of Ultrathin Films of Conductive Metal-Organic Frameworks.

Conductive metal-organic frameworks are opening new perspectives for the use of these porous materials for applications traditionally limited to more classical inorganic materials, such as their integration into electronic devices. This has enabled the development of chemiresistive sensors capable of transducing the presence of specific guests into an electrical response with good selectivity and sensitivity. By combining experimental data with computational modelling, a possible origin for the underlying mechanism of this phenomenon in ultrathin films (ca. 30 nm) of Cu-CAT-1 is described.

High-Quality Metal-Organic Framework Ultrathin Films for Electronically Active Interfaces.

Currently available methodologies arguably lack the exquisite control required for producing metal-organic framework (MOF) thin films of sufficient quality for electronic applications. By directing MOF transfer with self-assembled monolayers (SAMs), we achieve very smooth, homogeneous, highly oriented, ultrathin films across millimeter-scale areas that display moderate conductivity likely due to electron hopping. Here, the SAM is key for directing the transfer thereby enlarging the number and nature of the substrates of choice. We have exploited this versatility to evolve from deposition onto standard Si and Au to nonconventional substrates such as ferromagnetic Permalloy. We believe that this strategy might be useful for the integration of MOFs as active interfaces in electronic devices.

Self-assembled monolayers on a ferromagnetic permalloy surface.

Self-assembled monolayers (SAMs) are nowadays broadly used as surface protectors or modifiers and play a key role in many technological applications. This has motivated the study of their formation in all kind of materials; however, and despite the current interest in molecular spintronics, the study of SAMs on ferromagnetic surfaces remains almost unexplored. In this paper, we report for the first time a methodology for the formation of SAMs of n-alkylphosphonic acids on permalloy in ambient conditions. The formed monolayers have been fully characterized by means of contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, matrix assisted laser desorption ionization time-of-flight mass spectrometry, infrared reflection absorption spectroscopy, and X-ray reflectometry. Additionally, the magnetic stability of the modified permalloy after the solution process required for the SAM formation has been confirmed by magneto-optical Kerr effect magnetometry. Moreover, by means of microcontact printing lithography, very accurate SAM patterns have been transferred onto permalloy surfaces and used as resist mask in a chemical etching process giving rise to submicrometric permalloy surface patterns with potential interest in nanomagnetism, spintronics, and storage technologies.

Effect of metal complexation on the conductance of single-molecular wires measured at room temperature.

The present work aims to give insight into the effect that metal coordination has on the room-temperature conductance of molecular wires. For that purpose, we have designed a family of rigid, highly conductive ligands functionalized with different terminations (acetylthiols, pyridines, and ethynyl groups), in which the conformational changes induced by metal coordination are negligible. The single-molecule conductance features of this series of molecular wires and their corresponding Cu(I) complexes have been measured in break-junction setups at room temperature. Experimental and theoretical data show that no matter the anchoring group, in all cases metal coordination leads to a shift toward lower energies of the ligand energy levels and a reduction of the HOMO-LUMO gap. However, electron-transport measurements carried out at room temperature revealed a variable metal coordination effect depending on the anchoring group: upon metal coordination, the molecular conductance of thiol and ethynyl derivatives decreased, whereas that of pyridine derivatives increased. These differences reside on the molecular levels implied in the conduction. According to quantum-mechanical calculations based on density functional theory methods, the ligand frontier orbital lying closer to the Fermi energy of the leads differs depending on the anchoring group. Thereby, the effect of metal coordination on molecular conductance observed for each anchoring could be explained in terms of the different energy alignments of the molecular orbitals within the gold Fermi level.

Bioinspired catechol-terminated self-assembled monolayers with enhanced adhesion properties.

The role of the catechol moiety in the adhesive properties of mussel proteins and related synthetic materials has been extensively studied in the last years but still remains elusive. Here, a simplified model approach is presented based on a self-assembled monolayer (SAM) of upward-facing catechols thiol-bound to epitaxial gold substrates. The orientation of the catechol moieties is confirmed by spectroscopy, which also showed lack of significant amounts of interfering o-quinones. Local force-distance curves on the SAM measured by atomic force microscopy (AFM) shows an average adhesion force of 45 nN, stronger than that of a reference polydopamine coating, along with higher reproducibility and less statistical dispersion. This is attributed to the superior chemical and topographical homogeneity of the SAM coating. Catechol-terminated SAMs are also obtained on high-roughness gold substrates that show the ability to assemble magnetic nanoparticles, despite their lack of enhanced adhesion at the molecular level. Finally, the influence of the catechol group on the formation and quality of the SAM is explored both theoretically (molecular dynamics simulations) and experimentally using direct-write AFM lithography.

Fast pirouetting motion in a pyridine bisamine-containing copper-complexed rotaxane.

The present work reports the introduction of pyridine bisamine terdentate ligands in the structure of a pirouetting copper rotaxane. Rotaxane 2[PF6] constitutes the first example of the incorporation of imine-based dynamic covalent chemistry in the synthesis of switchable copper-complexed interlocked systems. In this rotaxane, the substitution of the classical terpyridine terdentate unit by a pyridine bisamine moiety has led to a significant stabilization of the pentacoordinated site. That fact has been evidenced by EPR spectroscopy and cyclic voltammetry. Regarding the tetracoordinated site, the congestion around the coordination sphere has been reduced to accelerate the typically slow reorganization of the Cu(II). Ethynyl-3,8-substitution on the axis phenanthroline along with the 2,9-diphenyl-1,10-phenanthroline (dpp) present in the macrocycle afforded a very stable coordination environment for Cu(I), which is at the same time labile upon oxidation. In summary, the incorporation of a pyridine bisamine unit as a terdentate ligand and the optimization of the bidentate ligand of the axle not only has led to a simplification of the synthetic procedures, but it has also given rise to a bistable systems with an enhanced energetic separation between states and an acceleration of the reorganization processes. Thus far, rotaxane 2[PF6] presents the fastest switching cycle reported to date in copper-interlocked dynamic systems.

Fast redox-triggered shuttling motions in a copper rotaxane based on a phenanthroline-terpyridine conjugate.

Fast shuttling motions in solution have been observed by cyclic voltammetry in a Cu(I/II)-based [2] rotaxane. In the reported system, the different coordination preferences of both copper oxidation states are exploited to promote the electrochemically-triggered gliding of the ring from a tetra to a pentacoordinated site and vice versa. The thread of this rotaxane consists of a tridentate 2,2':6',2''-terpyridine chelating unit directly bonded through its 5-position to the 3-position of the bidentate 1,10-phenanthroline unit. This distribution reduces to a minimum the distance between the two coordination sites and lessens the congestion around the tetrahedral environment. These two factors have been demonstrated to highly increase the kinetics of the switching process. In addition, the electrochemical experiments carried out in different solvent mixtures evidenced the influence of the solvent on the shuttling mechanism.