Carlos Martí-Gastaldo

Carlos Martí-Gastaldo
University of Valencia | UV · Instituto de Ciencia Molecular (ICMol)

MSc PhD Chemistry

About

167
Publications
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7,877
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Additional affiliations
January 2012 - present
University of Liverpool
January 2005 - August 2009
University of Valencia

Publications

Publications (167)
Article
Pepped up: Notwithstanding the intrinsic conformational flexibility of peptides, [Zn(Gly-Thr)(2) ] behaves as a robust porous metal-organic framework thanks to the rigidity introduced by the use of Gly-Thr. This rigidity arises from the sequence of amino acids in the dipeptide that locks its conformational flexibility in the framework.
Article
Although the coexistence of superconductivity and ferromagnetism in one compound is rare, some examples of such materials are known to exist. Methods to physically prepare hybrid structures with both competing phases are also known, which rely on the nanofabrication of alternating conducting layers. Chemical methods of building up hybrid materials...
Article
The anionic oxalate-bridged bimetallic chain [Co(H2O)2Cr(ox)3]- shows slow relaxation of the magnetization, typical of the so-called single-chain magnets, when crystallized in segregated layers in a mixed salt with the supramolecular cations [C12H24O6K]+ and [(C12H24O6)(FC6H4NH3)]+. This is the first time that such phenomenon has been observed in a...
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Full-text available
The structural and compositional diversification of Metal‐Organic Frameworks (MOFs) continues to grow, along with the opportunities they offer in H₂ photoevolution or CO₂ photoreduction. This often requires the use of metal co‐catalysts for improving the efficiency and selectivity of the reaction. However, most studies often overlook how the integr...
Article
The soft nature of Metal‐Organic Frameworks (MOFs) sets them apart from other non‐synthetic porous materials. Their flexibility allows the framework components to rearrange in response to environmental changes, leading to different states and properties. The work extends this concept to titanium frameworks, demonstrating control over charge transpo...
Article
Porphyrinic metal-organic frameworks (MOFs) offer high surface areas and tunable catalytic and optoelectronic properties, making them versatile candidates for applications in phototherapy, drug delivery, photocatalysis, electronics, and energy storage. However, a key challenge for industrial integration is the rapid, cost-effective production of su...
Article
Reticular chemistry has in the post-synthetic modification (PSM) of frameworks one of the most versatile tools to adapt the systems' physicochemical properties to the specific requirements which are imposed by their application in different contexts. We can safely say that PSM methodologies in all their variants are currently one of the main resour...
Preprint
The increasing use of Metal-Organic Frameworks (MOFs) in separation, catalysis or storage is linked to the targeted modifi-cation of their composition or porosity metrics. While modification of pore shape and size necessarily implies the assembly of alternative nets, compositional changes often rely on post-synthetic modification adapted to the fun...
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Full-text available
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...
Article
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 CO 2 capture. In this study, we propose an alternative mechanism that does not rely on the use of neutral metal vacancies as binding sites...
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The combination of compositional versatility and topological diversity for the integration of electroactive species into high-porosity molecular architectures is perhaps one of the main appeals of metal–organic frameworks (MOFs) in the field of electrocatalysis. This premise has attracted much interest in recent years, and the results generated hav...
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Full-text available
Metal–organic frameworks (MOFs) are a rapidly growing class of materials that offer great promise in various applications. However, the synthesis remains challenging: for example, a range of crystal structures can often be accessed from the same building blocks, which complicates the phase selectivity. Likewise, the high sensitivity to slight chang...
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Full-text available
Among the multiple applications of metal–organic frameworks (MOFs), their use as a porous platform for the support of metallic nanoparticles stands out for the possibility of integrating a good anchorage, that improves the stability of the catalyst, with the presence of a porous network that allows the diffusion of substrates and products. Here we...
Article
Heterobimetallic Metal–Organic Frameworks (MOFs) synergically combine the properties of two metal ions, thus offering significant advantages over homometallic MOFs in gas storage, separation, and catalysis, among other applications. However, these remain centered on bulk materials, while applications that require functional coatings on solid suppor...
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Full-text available
Changing the perception of defects as imperfections in crystalline frameworks into correlated domains amenable to chemical control and targeted design might offer opportunities for the design of porous materials with superior performance or distinctive behavior in catalysis, separation, storage, or guest recognition. From a chemical standpoint, the...
Article
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 d...
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The presence of tetrazine units in the organic nodes of UiO‐68‐TZCD controls the formation of ultrathin coatings of single‐wall nanotubes that decorate the surface of the crystal. These crystal hybrids can be prepared straightforwardly in one step and are extraordinarily respectful with the properties of the framework for combination of mesoporosit...
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The modular synthesis approach for assembling inorganic nodes and organic multidentate linkers into reticular solids enables rational engineering in porous materials known as metal–organic frameworks (MOFs). Incorporation of two or more linker types in MOF crystals holds great potential for engineering complex pore functionalities, by virtue of che...
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Research on metal-organic frameworks is shifting from the principles that control the assembly, structure, and porosity of these reticular solids, already established, into more sophisticated concepts that embrace chemical complexity as a tool for encoding their function or accessing new properties by exploiting the combination of different compone...
Preprint
Full-text available
Metal--organic frameworks (MOFs) are a rapidly growing class of materials that offer great promise in various applications. However, the synthesis remains challenging: for example, a range of crystal structures can often be accessed from the same building blocks, which complicates the phase selectivity. Likewise, the high sensitivity to slight chan...
Article
Full-text available
A quantum spin liquid (QSL) is an elusive state of matter characterized by the absence of long-range magnetic order, even at zero temperature, and by the presence of exotic quasiparticle excitations. In spite of their relevance for quantum communication, topological quantum computation and the understanding of strongly correlated systems, like high...
Preprint
Full-text available
The presence of tetrazine units in the organic nodes of UiO- 68-TZCD controls the formation of ultrathin coatings of single wall nanotubes that decorate the surface of the crystal. These crystal hybrids can be prepared straightforwardly in one step and are extraordinarily respectful with the properties of the framework for combination of mesoporosi...
Article
Full-text available
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 a...
Preprint
Full-text available
Changing the perception of defects as irregularities or imperfections in crystalline frameworks into correlated domains amenable to chemical control and targeted design might offer unprecedented opportunities for the design of porous materials with superior performance or distinctive behavior in catalysis, separation, storage, or guest recognition....
Article
Rationalizing the role of chemical functionalisation on the synergy between spin crossover (SCO) and guest adsorption properties in porous FeII coordination polymers is a central topic within the switchable materials...
Article
Full-text available
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 result...
Article
The design of antiferromagnetic nanomaterials preserving large orbital magnetic moments is important to protect their functionalities against magnetic perturbations. Here, we exploit an archetype H6HOTP species for conductive metal-organic frameworks to design a Co-HOTP one-atom-thick metal-organic architecture on a Au(111) surface. Our multidiscip...
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Full-text available
Photocatalysis process is a promising technology for environmental remediation. In the continuous search of new heterogeneous photocatalysts, metal–organic frameworks (MOFs) have recently emerged as a new type of photoactive materials for water remediation. Particularly, titanium-based MOFs (Ti-MOFs) are considered one of the most appealing subclas...
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Full-text available
The synthesis of crystalline one-dimensional polymers provides a fundamental understanding about the structure-property relationship in polymeric materials and allows the preparation of materials with enhanced thermal, mechanical, and conducting properties. However, the synthesis of crystalline one-dimensional polymers remains a challenge because p...
Article
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 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 tet...
Article
Full-text available
Nanoporous Materials In article number 2201502, David Fairen‐Jimenez and co‐workers conduct a round‐robin exercise by providing 18 already‐measured adsorption isotherms to sixty‐one labs and show that the reproducibility of the Brunauer–Emmett–Teller (BET) area determination in micro‐ and mesoporous materials remains a largely ignored issue. To sol...
Article
Full-text available
Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the est...
Preprint
Full-text available
Photocatalysis process is a promising technology for environmental remediation. In the continuous search of new heterogeneous photocatalysts, metal-organic frameworks (MOFs) have recently emerged as a new type of photoactive materials for water remediation. Particularly, titanium-based MOFs (Ti-MOFs) are considered one of the most appealing subclas...
Article
Full-text available
Defect engineering is a valuable tool to tune the photocatalytic activity of metal-organic frameworks (MOFs). Inducing defects through the attachment of functionalized modulators can introduce cooperative units that can tune the bandgap of the material and enhance their chemical, thermal, and photostabilities among other properties. However, the ma...
Article
We investigate the use of a series of iron-based metal−organic frameworks as precursors for the manufacturing of isobutane dehydrogenation catalysts. Both the as-prepared and spent catalysts were characterized by PXRD, XPS, PDF, ICP-OES, and CHNS+O to determine the physicochemical properties of the materials and the active phases responsible for th...
Preprint
Full-text available
Porosity and surface area analysis play a prominent role in modern materials science, where their determination spans the fields of natural sciences, engineering, geology and medical research. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory,[1] which has been a remarkably successful contribution to the field of materials science....
Article
Full-text available
Following the synthesis of hydroxamate titanium-organic frameworks, we now extend these siderophore-type linkers to the assembly of the first titanium-organic polyhedra displaying permanent porosity. Mixed-linker versions of this molecular cage (cMUV-11) are also used to demonstrate the effect of pore chemistry in accessing high surface areas of ne...
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Biotemplating is a powerful approach for manufacturing small-scale devices. Here, the assembly of metal–organic framework (MOF) nanocrystals onto biotemplated magnetic helical structures on the cyanobacterium Spirulina platensis is reported. It is demonstrated that the authors’ approach is universal and can be used to equip biotemplated structures...
Article
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Two‐dimensional fused aromatic networks (2D FANs) have emerged as a highly versatile alternative to holey graphene. The synthesis of 2D FANs with increasingly larger lattice dimensions will enable new application perspectives. However, the synthesis of larger analogues is mostly limited by lack of appropriate monomers and methods. Herein, we descri...
Article
Two-dimensional fused aromatic networks (2D FANs) have emerged as a highly versatile alternative to holey graphene. The synthesis of 2D FANs with increasingly larger lattice dimensions will enable new application perspectives. However, the synthesis of larger analogs is mostly limited by lack of appropriate monomers and methods. Herein, we describe...
Article
We use dodecanoic acid as a modulator to yield titanium MOF nanoparticles with good control of size and colloid stability and minimum impact to the properties of the framework to...
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Full-text available
Defect engineering is a valuable tool to tune the properties of metal-organic frameworks. However, defect chemistry remains still predominantly limited to UiO-type MOFs. We describe the preferential formation of missing cluster defects in heterometallic titanium-organic frameworks of the MUV-10 family when synthesised in sub-stoichiometric linker c...
Preprint
Full-text available
We use dodecanoic acid as a modulator to yield titanium MOF nanoparticles with good control of size and colloid stability and minimum impact to the properties of the framework to enable direct fabrication of crystalline, porous thin films
Preprint
Full-text available
We use dodecanoic acid as a modulator to yield titanium MOF nanoparticles with good control of size and colloid stability and minimum impact to the properties of the framework to enable direct fabrication of crystalline, porous thin films
Article
The Ti-Ca heterometallic MOF MUV-10 exhibits good dispersibility in phosphate buffer and low phosphate-induced degradation in comparison to other MOF systems. It induces no cytotoxicity towards cells of the immune system and no inmune response, making it an attractive candidate for biomedical applications and demonstrating its safe use for other ap...
Article
Their complex surface chemistry and high oxygen lattice mobilities place mixed-metal oxides among the most important families of materials. Modulation of stoichiometry in mixed-metal oxides has been shown to be a very powerful tool for tuning optical and catalytic properties. However, accessing different stoichiometries is not always synthetically...
Preprint
Full-text available
Porosity and surface area analysis play a prominent role in modern materials science, where 123 their determination spans the fields of natural sciences, engineering, geology and medical 124 research. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory,[1] which has been 125 a remarkably successful contribution to the field of materia...
Article
Full-text available
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 cy...
Article
A selective grafting route for heterometallic MOFs is described by Carlos Martí‐Gastaldo and co‐workers in their Research Article (DOI: 10.1002/anie.202100176). The different chemistry of Ti(IV) and Ca(II) sites is used to direct selective coordination of amines to the latter. This enables the combination of Lewis acid titanium centers and availabl...
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Full-text available
Three‐dimensional covalent organic frameworks (3D COFs) with a pcu topology have been obtained from distorted polycyclic aromatic hydrocarbons acting as triangular antiprismatic (D3d) nodes. Such 3D COFs are six‐fold interpenetrated as the result of interframework π‐stacking, which enable charge transport properties that are not expected for 3D COF...
Article
Selektives Grafting wird von Carlos Martí‐Gastaldo und Mitarbeitern in ihrem Forschungsartikel (DOI: 10.1002/anie.202100176) für die Synthese heterometallischer MOFs verwendet. Die unterschiedliche Chemie von Ti(IV)‐ und Ca(II)‐Zentren wird genutzt, um eine selektive Koordination von Aminen an die Ca(II)‐Zentren zu bewirken. Dies ermöglicht die Kom...
Article
The different affinity of Ti(IV) and Ca(II) sites to direct selective coordination of amines was used. This enables the combination of Lewis acid and available ‐NH2 sites in sizeable pores for cooperative cycloaddition of CO2 to epoxides. MUV‐12 displays full conversion of propylene oxide at room temperature and atmospheric pressure in absence of a...
Article
A new wavy 2D covalent organic framework shines light on the structural factors that dominate charge transport.
Article
Three‐dimensional covalent organic frameworks (3D COFs) have been obtained from distorted polycyclic aromatic hydrocarbon nodes. Interframework π‐stacking enables charge transport properties that are not expected for 3D COFs. Abstract Three‐dimensional covalent organic frameworks (3D COFs) with a pcu topology have been obtained from distorted poly...
Article
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 Zr 6-M...
Article
We report a crystalline supramolecular framework assembled by H-bonding interactions between covalently fused monomers equipped with two guanine-cytosine nucleobase pairs.
Article
Room temperature one-step synthesis of the peptide-based porous material with a periodic distribution of pockets decorated with lysine side chain active sites behaves as a heterogeneous organocatalyst. The pockets are...
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Full-text available
The recognition of defect chemistry as a true synthetic tool for targeted creation of defects and controllable performance remains limited by the pool of frameworks explored. The value of defect engineering in controlling the properties of defective frameworks has been beautifully exemplified and largely demonstrated with UiO-type materials based o...
Article
Zn-containing metal-organic frameworks have been used for the first time as heterogeneous catalysts in the amination of C-Cl bonds. The use of extended bis(pyrazolate) linkers can generate highly porous architectures, which favor the diffusion of amines to the confined spaces with respect to other imidazolate frameworks with narrower pore windows....
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Full-text available
A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the population γHS(T) with high-spin (HS)-low-spin (LS) sequence: HS1LS0 (state 1) ↔ HS2/3LS1/3 (state 2) ↔ HS1/2LS1/2 (state 3) ↔ HS1/3LS2/3 (state 4) ↔ HS0LS1 (state 5), and complete one step hysteretic spin transition featuring 20 K wide...
Article
Mixed-metal or heterometallic metal-organic frameworks (MOFs) are gaining importance as a route to produce materials with increasing chemical and functional complexities. We report a family of heterometallic titanium frameworks, MUV-101(M), and use them to exemplify the advantages of controlling metal distribution across the framework in heterogene...
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Full-text available
Spin crossover (SCO) compounds are very attractive types of switchable materials due to their potential applications in memory devices, actuators or chemical sensors. Rational chemical tailoring of these switchable compounds is key for achieving new functionalities in synergy with the spin state change. However, the lack of precise structural infor...
Article
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 ni...
Article
Integration of the ON-OFF cooperative spin crossover (SCO) properties of FeII coordination polymers as components of electronic and/or spintronic devices is currently an area of great interest for potential applications. This requires the selection and growth of thin films of the appropriate material onto selected substrates. In this context, two n...
Article
To control and understand the mechanisms that harness crystallization processes is of utmost importance in contemporary materials science and in particular in the realm of reticular solids where it still remains a great challenge. In this work, we show that environments mimicking microgravity conditions can harness the size and shape of functional...
Article
A novel gas sensing mechanism exploiting lanthanide luminescence modulation upon NO2 adsorption is here demonstrated. Two isostructural lanthanide-based metal-organic frameworks are used including a recognition center (amino-group) that provides high selectivity for NO2 molecules. Energy transfer from the organic ligands to Ln is strongly dependent...
Article
Reticular chemistry has boosted the design of thousands of Metal and Covalent Organic Frameworks for unlimited chemical compositions, structures and sizeable porosities. The ability to generate porous materials at will based on geometrical design concepts is responsible for the rapid growth of the field and the increasing number of applications der...