Interplay between the oxidation process and cytotoxic effects of antimonene nanomaterials.

Pnictogen nanomaterials have recently attracted researchers' attention owing to their promising properties in the field of electronic, energy storage, and nanomedicine applications. Moreover, especially in the case of heavy pnictogens, their chemistry allows for nanomaterial synthesis using both top-down and bottom-up approaches, yielding materials with remarkable differences in terms of morphology, size, yield, and properties. In this study, we carried out a comprehensive structural and spectroscopic characterization of antimony-based nanomaterials (Sb-nanomaterials) obtained by applying different production methodologies (bottom-up and top-down routes) and investigating the influence of the synthesis on their oxidation state and stability in a biological environment. Indeed, in situ XANES/EXAFS studies of Sb-nanomaterials incubated in cell culture media were carried out, unveiling a different oxidation behavior. Furthermore, we investigated the cytotoxic effects of Sb-nanomaterials on six different cell lines: two non-cancerous (FSK and HEK293) and four cancerous (HeLa, SKBR3, THP-1, and A549). The results reveal that hexagonal antimonene (Sb-H) synthesized using a colloidal approach oxidizes the most and faster in cell culture media compared to liquid phase exfoliated (LPE) antimonene, suffering acute degradation and anticipating well-differentiated toxicity from its peers. In addition, the study highlights the importance of the synthetic route for the Sb-nanomaterials as it was observed to influence the chemical evolution of Sb-H into toxic Sb oxide species, playing a critical role in its ability to rapidly eliminate tumor cells. These findings provide insights into the mechanisms underlying the dark cytotoxicity of Sb-H and other related Sb-nanomaterials, underlining the importance of developing therapies based on controlled and on-demand nanomaterial oxidation.

Engineering Metal Halide Perovskite Nanocrystals with BODIPY Dyes for Photosensitization and Photocatalytic Applications.

The sensitization of surface-anchored organic dyes on semiconductor nanocrystals through energy transfer mechanisms has received increasing attention owing to their potential applications in photodynamic therapy, photocatalysis, and photon upconversion. Here, we investigate the sensitization mechanisms through visible-light excitation of two nanohybrids based on CsPbBr3 perovskite nanocrystals (NC) functionalized with borondipyrromethene (BODIPY) dyes, specifically 8-(4-carboxyphenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP) and 8-(4-carboxyphenyl)-2,6-diiodo-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (I2-BDP), named as NC@BDP and NC@I2-BDP, respectively. The ability of I2-BDP dyes to extract hot hole carriers from the perovskite nanocrystals is comprehensively investigated by combining steady-state and time-resolved fluorescence as well as femtosecond transient absorption spectroscopy with spectroelectrochemistry and quantum chemical theoretical calculations, which together provide a complete overview of the phenomena that take place in the nanohybrid. Förster resonance energy transfer (FRET) dominates (82%) the photosensitization of the singlet excited state of BDP in the NC@BDP nanohybrid with a rate constant of 3.8 ± 0.2 × 1010 s-1, while charge transfer (64%) mediated by an ultrafast charge transfer rate constant of 1.00 ± 0.08 × 1012 s-1 from hot states and hole transfer from the band edge is found to be mainly responsible for the photosensitization of the triplet excited state of I2-BDP in the NC@I2-BDP nanohybrid. These findings suggest that the NC@I2-BDP nanohybrid is a unique energy transfer photocatalyst for oxidizing α-terpinene to ascaridole through singlet oxygen formation.

Few-layer black phosphorus enables nitrogen fixation under ambient conditions.

Nitrogen (N2) fixation is a key reaction in biological and industrial chemistry, which does not occur spontaneously under ambient conditions but often depends on very specific catalysts and harsh reaction processes. Here we show that exposing exfoliated black phosphorus to the open air triggers, concomitantly, the oxidation of the two-dimensional (2D) material and the fixation of up to 100 parts per million (0.01%) of N2 on the surface. The fixation also occurs in pristine non-exfoliated material. Besides, other allotropic forms of phosphorus, like red P, also fixes N2 during ambient oxidation, suggesting that the N2 fixation process is intrinsic with phosphorus oxidation and does not depend on the chemical structure or the dimensionality of the solid. Despite the low amounts of N2 fixed, this serendipitous discovery could have fundamental implications on the chemistry and environmental stability of phosphorous and the design of related catalysts for N2 fixation.

Influence of Crystallographic Structure and Metal Vacancies on the Oxygen Evolution Reaction Performance of Ni-based Layered Hydroxides.

Nickel-based layered hydroxides (LHs) are a family of efficient electrocatalysts for the alkaline oxygen evolution reaction (OER). Nevertheless, fundamental aspects such as the influence of the crystalline structure and the role of lattice distortion of the catalytic sites remain poorly understood and typically muddled. Herein, we carried out a comprehensive investigation on ɑ-LH, ß-LH and layered double hydroxide (LDH) phases by means of structural, spectroscopical, in-silico and electrochemical studies, which suggest the key aspect exerted by Ni-vacancies in the ɑ-LH structure. Density functional theory (DFT) calculations and X-ray absorption spectroscopy (XAS) confirm that the presence of Ni-vacancies produces acute distortions of the electroactive Ni sites (reflected as the shortening of the Ni-O distances and changes in the O-Ni-O angles), triggering the appearance of Ni localised electronic states on the Fermi level, reducing the Egap, and consequently, increasing the reactivity of the electroactive sites in the ɑ-LH structure. Furthermore, post-mortem Raman and XAS measurements unveil its transformation into a highly reactive oxyhydroxide-like phase that remains stable under ambient conditions. Hence, this work pinpoints the critical role of the crystalline structure as well as the electronic properties of LH structures on their inherent electrochemical reactivity towards OER catalysis. We envision Ni-based ɑ-LH as a perfect platform for hosting trivalent cations, closing the gap toward the next generation of benchmark efficient earth-abundant electrocatalysts.

"On-The-Fly" Synthesis of Self-Supported LDH Hollow Structures Through Controlled Microfluidic Reaction-Diffusion Conditions.

Layered double hydroxides (LDHs) are a class of functional materials that exhibit exceptional properties for diverse applications in areas such as heterogeneous catalysis, energy storage and conversion, and bio-medical applications, among others. Efforts have been devoted to produce millimeter-scale LDH structures for direct integration into functional devices. However, the controlled synthesis of self-supported continuous LDH materials with hierarchical structuring up to the millimeter scale through a straightforward one-pot reaction method remains unaddressed. Herein, it is shown that millimeter-scale self-supported LDH structures can be produced by means of a continuous flow microfluidic device in a rapid and reproducible one-pot process. Additionally, the microfluidic approach not only allows for an "on-the-fly" formation of unprecedented LDH composite structures, but also for the seamless integration of millimeter-scale LDH structures into functional devices. This method holds the potential to unlock the integrability of these materials, maintaining their performance and functionality, while diverging from conventional techniques like pelletization and densification that often compromise these aspects. This strategy will enable exciting advancements in LDH performance and functionality.

Novel side chain functionalized polystyrene/O-PBI blends with high alkaline stability for anion exchange membrane water electrolysis (AEMWE).

We report the synthesis of a polystyrene-based anion exchange polymer bearing the cationic charge at a C6-spacer. The polymer is prepared by a functionalized monomer strategy. First, a copper halide catalyzed C-C coupling reaction between a styryl Grignard and 1,6-dibromohexane is applied, followed by quaternization with N-methylpiperidine and free radical polymerization. The novel polymer is blended with the polybenzimidazole O-PBI to yield mechanically stable blend membranes representing a new class of anion exchange membranes. In this regard, the ratio of the novel anion exchange polymer to O-PBI is varied to study the influence on water uptake and ionic conductivity. Blend membranes with IECs between 1.58 meq. OH- g-1 and 2.20 meq. OH- g-1 are prepared. The latter shows excellent performance in AEMWE, reaching 2.0 A cm-2 below 1.8 V in 1 M KOH at 70 °C, with a minor degradation rate from the start. The blend membranes show no conductivity loss after immersion in 1 M KOH at 85 °C for six weeks indicating high alkaline stability.

Upscaling the urea method synthesis of CoAl layered double hydroxides.

Research on two-dimensional materials is one of the most relevant fields in materials science. Layered double hydroxides (LDHs), a versatile class of anionic clays, exhibit great potential in photocatalysis, energy storage and conversion, and environmental applications. However, its implementation in real-life devices requires the development of efficient and reproducible large-scale synthesis processes. Unfortunately, reliable methods that allow for the production of large quantities of two-dimensional LDHs with well-defined morphologies and high crystallinity are very scarce. In this work, we carry out a scale-up of the urea-based CoAl-LDH synthesis method. We thoroughly study the effects of the mass scale-up (25-fold: up to 375 mM) and the volumetric scale-up (20-fold: up to 2 L). For this, we use a combination of several structural (XRD, TGA, and N2 and CO2 isotherms), microscopic (SEM, TEM, and AFM), magnetic (SQUID), and spectroscopic techniques (ATR-FTIR, UV-vis, XPS, ICP-MS, and XANES-EXAFS). In the case of the volumetric scale-up, a reduction of 45% in the lateral dimensions of the crystals (from 3.7 to 2.0 µm) is observed as the reaction volume increases. This fact is related to modified heating processes affecting the alkalinization rates and, concomitantly, the precipitation, even under recrystallization at high temperatures. In contrast, for the tenfold mass scale-up, similar morphological features were observed and assigned to changes in nucleation and growth. However, at higher concentrations, simonkolleite-like Co-based layered hydroxide impurities are formed, indicating a phase competition during the precipitation related to the thermodynamic stability of the growing phases. Overall, this work demonstrates that it is possible to upscale the synthesis of high-quality hexagonal CoAl-LDH in a reproducible manner. It highlights the most critical synthesis aspects that must be controlled and provides various fingerprints to trace the quality of these materials. These results will contribute to bringing the use of these 2D layered materials closer to reality in different applications of interest.

Crystallographic and Geometrical Dependence of Water Oxidation Activity in Co-Based Layered Hydroxides.

Cobalt-based layered hydroxides (LHs) stand out as one of the best families of electroactive materials for the alkaline oxygen evolution reaction (OER). However, fundamental aspects such as the influence of the crystalline structure and its connection with the geometry of the catalytic sites remain poorly understood. Thus, to address this topic, we have conducted a thorough experimental and in silico study on the most important divalent Co-based LHs (i.e., α-LH, ß-LH, and LDH), which allows us to understand the role of the layered structure and coordination environment of divalent Co atoms on the OER performance. The α-LH, containing both octahedral and tetrahedral sites, behaves as the best OER catalyst in comparison to the other phases, pointing out the role of the chemical nature of the crystalline structure. Indeed, density functional theory (DFT) calculations confirm the experimental results, which can be explained in terms of the more favorable reconstruction into an active Co(III)-based oxyhydroxide-like phase (dehydrogenation process) as well as the significantly lower calculated overpotential across the OER mechanism for the α-LH structure (exhibiting lower Egap). Furthermore, ex situ X-ray diffraction and absorption spectroscopy reveal the permanent transformation of the α-LH phase into a highly reactive oxyhydroxide-like stable structure under ambient conditions. Hence, our findings highlight the key role of tetrahedral sites on the electronic properties of the LH structure as well as their inherent reactivity toward OER catalysis, paving the way for the rational design of more efficient and low-maintenance electrocatalysts.

Hexagonal Hybrid Bismuthene by Molecular Interface Engineering.

High-quality devices based on layered heterostructures are typically built from materials obtained by complex solid-state physical approaches or laborious mechanical exfoliation and transfer. Meanwhile, wet-chemically synthesized materials commonly suffer from surface residuals and intrinsic defects. Here, we synthesize using an unprecedented colloidal photocatalyzed, one-pot redox reaction a few-layers bismuth hybrid of "electronic grade" structural quality. Intriguingly, the material presents a sulfur-alkyl-functionalized reconstructed surface that prevents it from oxidation and leads to a tuned electronic structure that results from the altered arrangement of the surface. The metallic behavior of the hybrid is supported by ab initio predictions and room temperature transport measurements of individual nanoflakes. Our findings indicate how surface reconstructions in two-dimensional (2D) systems can promote unexpected properties that can pave the way to new functionalities and devices. Moreover, this scalable synthetic process opens new avenues for applications in plasmonics or electronic (and spintronic) device fabrication. Beyond electronics, this 2D hybrid material may be of interest in organic catalysis, biomedicine, or energy storage and conversion.

Chemistry of two-dimensional pnictogens: emerging post-graphene materials for advanced applications.

The layered allotropes of group 15 (P, As, Sb and Bi), also called two-dimensional (2D) pnictogens, have emerged as one of the most promising families of post-graphene 2D-materials. This is mainly due to the great variety of properties they exhibit, including layer-dependent bandgap, high charge-carrier mobility and current on/off ratios, strong spin-orbit coupling, wide allotropic diversity and pronounced chemical reactivity. These are key ingredients for exciting applications in (opto)electronics, heterogeneous catalysis, nanomedicine or energy storage and conversion, to name a few. However, there are still many challenges to overcome in order to fully understand their properties and bring them to real applications. As a matter of fact, due to their strong interlayer interactions, the mechanical exfoliation (top-down) of heavy pnictogens (Sb & Bi) is unsatisfactory, requiring the development of new methodologies for the isolation of single layers and the scalable production of high-quality flakes. Moreover, due to their pronounced chemical reactivity, it is necessary to develop passivation strategies, thus preventing environmental degradation, as in the case of bP, or controlling surface oxidation, with the corresponding modification of the interfacial and electronic properties. In this Feature Article we will discuss, among others, the most important contributions carried out in our group, including new liquid phase exfoliation (LPE) processes, bottom-up colloidal approaches, the preparation of intercalation compounds, innovative non-covalent and covalent functionalization protocols or novel concepts for potential applications in catalysis, electronics, photonics, biomedicine or energy storage and conversion. The past years have seen the birth of the chemistry of pnictogens at the nanoscale, and this review intends to highlight the importance of the chemical approach in the successful development of routes to synthesise, passivate, modify, or process these materials, paving the way for their use in applications of great societal impact.

Antimonene: a tuneable post-graphene material for advanced applications in optoelectronics, catalysis, energy and biomedicine.

The post-graphene era is undoubtedly marked by two-dimensional (2D) materials such as quasi-van der Waals antimonene. This emerging material has a fascinating structure, exhibits a pronounced chemical reactivity (in contrast to graphene), possesses outstanding electronic properties and has been postulated for a plethora of applications. However, chemistry and physics of antimonene remain in their infancy, but fortunately recent discoveries have shed light on its unmatched allotropy and rich chemical reactivity offering a myriad of unprecedented possibilities in terms of fundamental studies and applications. Indeed, antimonene can be considered as one of the most appealing post-graphene 2D materials reported to date, since its structure, properties and applications can be chemically engineered from the ground up (both using top-down and bottom-up approaches), offering an unprecedented level of control in the realm of 2D materials. In this review, we provide an in-depth analysis of the recent advances in the synthesis, characterization and applications of antimonene. First, we start with a general introduction to antimonene, and then we focus on its general chemistry, physical properties, characterization and synthetic strategies. We then perform a comprehensive study on the allotropy, the phase transition mechanisms, the oxidation behaviour and chemical functionalization. From a technological point of view, we further discuss the applications recently reported for antimonene in the fields of optoelectronics, catalysis, energy storage, cancer therapy and sensing. Finally, important aspects such as new scalable methodologies or the promising perspectives in biomedicine are discussed, pinpointing antimonene as a cutting-edge material of broad interest for researchers working in chemistry, physics, materials science and biomedicine.

Two-dimensional magnetic behaviour in hybrid NiFe-layered double hydroxides by molecular engineering.

Layered double hydroxides (LDHs) are a class of two-dimensional (2D) anionic materials that exhibit remarkable chemical versatility, making them ideal building blocks in the design of complex multifunctional materials. In this line, a NiFe-LDH is probably one of the most important LDHs due to its interesting electrochemical and magnetic properties. However, no direct magnetic measurements of exfoliated NiFe-LDH nanosheets have been reported so far. Herein, we synthesize a hybrid NiFe-LDH family through anion exchange reactions using surfactant molecules in order to increase the interlayer space (ranging from 8 to 31.6 Å), minimizing the interlayer dipolar interactions. By intercalation with octadecylsulphate, we have managed to obtain the largest interlayer space reported for a NiFe-LDH while keeping a similar size, morphology and composition. This wide interlayer separation results in a decrease in temperatures at which spontaneous magnetization (TM) occurs and the blocking temperature (TB), as well as a decrease in the coercive fields (HC). In fact, an abrupt drop in all these magnetic parameters above 30 Å interlayer distance is observed, evidencing complete magnetic decoupling of the layers. We have further validated our molecular engineering approach by characterizing the hybrid materials by Mössbauer spectroscopy and comparing the magnetic analysis results with those for a liquid phase exfoliated NiFe-LDH sample. Overall, this work provides fundamental insights into the magnetism of NiFe-LDHs, showing the potential of molecular engineering for designing hybrid layered magnetic materials approaching the 2D magnetic limit.

Influence of Fe-clustering on the water oxidation performance of two-dimensional layered double hydroxides.

Among the two-dimensional (2D) materials family, layered double hydroxides (LDHs) represent a key member due to their unparalleled chemical versatility. In particular, Fe-based LDHs are distinguished candidates due to their high efficiency as oxygen evolution reaction (OER) electrocatalysts. Herein, we have selected MgFe-based LDH phases as model systems in order to decipher whether Fe-clustering exerts an effect on the OER performance. For that, we have optimized hydrothermal synthesis by using triethanolamine (TEA) as the chelating agent. The magnetic characterisation allows us to identify the Fe-clustering degree by following both magnetic susceptibility as well as magnetization values at 2 K. Thanks to this, we demonstrated that TEA induces an increment in Fe-clustering. Electrochemical OER measurements show that both samples behave identically by using glassy carbon electrodes. Interestingly, when the samples are tested in the most commonly employed electrode, nickel foam, striking differences arise. The sample exhibiting a lower Fe-clustering behaves as a better electrocatalyst with a reduction of the overpotential values of more than 50 mV to reach 100 mA cm-2, as a consequence of a favoured surface transformation of MgFe-LDHs phases into more reactive oxyhydroxide NiFe-based phases during the electrochemical tests. Hence, this work alerts about the importance of the electrocatalyst-electrode collector interactions which can induce misinterpretations in the OER performance.

Ruddlesden-Popper Hybrid Lead Bromide Perovskite Nanosheets of Phase Pure n=2: Stabilized Colloids Stored in the Solid State.

Ruddlesden-Popper lead halide perovskite (RP-LHP) nano-nanostructures can be regarded as self-assembled quantum wells or superlattices of 3D perovskites with an intrinsic quantum well thickness of a single or a few (n=2-4) lead halide layers; the quantum wells are separated by organic layers. They can be scaled down to a single quantum well dimension. Here, the preparation of highly (photo)chemical and colloidal stable hybrid LHP nanosheets (NSs) of ca. 7.4 µm lateral size and 2.5 nm quantum well height (thereby presenting a deep blue emission at ca. 440 nm), is reported for the first time. The NSs are close-lying and they even interconnect when deposited on a substrate. Their synthesis is based on the use of the p-toluenesulfonic acid/dodecylamine (pTS/DDA) ligand pair and their (photo)chemical stability and photoluminescence is enhanced by adding EuBr2 nanodots (EuNDs). Strikingly, they can be preserved as a solid and stored for at least one year. The blue emissive colloid can be recovered from the solid as needed by simply dispersing the powder in toluene and then using it to prepare solid films, making them very promising candidates for manufacturing devices.

Carbon Nano-onions: Potassium Intercalation and Reductive Covalent Functionalization.

Herein we report the synthesis of covalently functionalized carbon nano-onions (CNOs) via a reductive approach using unprecedented alkali-metal CNO intercalation compounds. For the first time, an in situ Raman study of the controlled intercalation process with potassium has been carried out revealing a Fano resonance in highly doped CNOs. The intercalation was further confirmed by electron energy loss spectroscopy and X-ray diffraction. Moreover, the experimental results have been rationalized with DFT calculations. Covalently functionalized CNO derivatives were synthesized by using phenyl iodide and n-hexyl iodide as electrophiles in model nucleophilic substitution reactions. The functionalized CNOs were exhaustively characterized by statistical Raman spectroscopy, thermogravimetric analysis coupled with gas chromatography and mass spectrometry, dynamic light scattering, UV-vis, and ATR-FTIR spectroscopies. This work provides important insights into the understanding of the basic principles of reductive CNOs functionalization and will pave the way for the use of CNOs in a wide range of potential applications, such as energy storage, photovoltaics, or molecular electronics.

Covalent and non-covalent chemistry of 2D black phosphorus.

The post-graphene era is undoubtedly marked by two-dimensional (2D) sheet polymers, such as black phosphorus (BP). This emerging material has a fascinating structure and outstanding electronic properties and has been postulated for a plethora of applications. The need to circumvent the pronounced oxophilicity of P atoms has dominated the research on this material in recent years, with the objective of finding the most effective method to improve its environmental stability. When it comes to chemical functionalization, the few approaches reported so far involve some drawbacks such as low degree of addition and low production ability. This review presents the concepts and strategies of our studies on the chemical functionalization of BP, both non-covalent and covalent, emphazising the current synthetic challenges. Moreover, we also provide some effective pathways for the chemical activation of the unreactive basal plane, the identification of the effective binding strategies, and the concept to overcome hurdles associated with characterization tools. This work will provide fundamental insights into the controlled chemical functionalization and characterization of BP, fostering the research on this appealing 2D material.

Acid Catalysis with Alkane/Water Microdroplets in Ionic Liquids.

Ionic liquids are composed of an organic cation and a highly delocalized perfluorinated anion, which remain tight to each other and neutral across the extended liquid framework. Here we show that n-alkanes in millimolar amounts enable a sufficient ion charge separation to release the innate acidity of the ionic liquid and catalyze the industrially relevant alkylation of phenol, after generating homogeneous, self-stabilized, and surfactant-free microdroplets (1-5 µm). This extremely mild and simple protocol circumvents any external additive or potential ionic liquid degradation and can be extended to water, which spontaneously generates microdroplets (ca. 3 µm) and catalyzes Brönsted rather than Lewis acid reactions. These results open new avenues not only in the use of ionic liquids as acid catalysts/solvents but also in the preparation of surfactant-free, well-defined ionic liquid microemulsions.

Exfoliation of Alpha-Germanium: A Covalent Diamond-Like Structure.

2D materials have opened a new field in materials science with outstanding scientific and technological impact. A largely explored route for the preparation of 2D materials is the exfoliation of layered crystals with weak forces between their layers. However, its application to covalent crystals remains elusive. Herein, a further step is taken by introducing the exfoliation of germanium, a narrow-bandgap semiconductor presenting a 3D diamond-like structure with strong covalent bonds. Pure α-germanium is exfoliated following a simple one-step procedure assisted by wet ball-milling, allowing gram-scale fabrication of high-quality layers with large lateral dimensions and nanometer thicknesses. The generated flakes are thoroughly characterized by different techniques, giving evidence that the new 2D material exhibits bandgaps that depend on both the crystallographic direction and the number of layers. Besides potential technological applications, this work is also of interest for the search of 2D materials with new properties.

Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts.

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, 31 P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.

The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd-Even Effect of the Organic Spacer.

A dramatic change in the magnetic behaviour, which solely depends on the parity of the organic linker molecules, has been found in a family of layered CoII hydroxides covalently functionalized with dicarboxylic molecules. These layered hybrid materials have been synthesized at room temperature using a one-pot procedure through the epoxide route. While hybrids connected by odd alkyl chains exhibit coercive fields (Hc ) below ca. 3500 Oe and show spontaneous magnetization at temperatures (TM ) below 20 K, hybrids functionalized with even alkyl chains behave as hard magnets with Hc >5500 Oe and display a TM higher than 55 K. This intriguing behaviour was studied by density functional theory with the incorporation of a Hubbard term (DFT+U) calculations, unveiling the structural subtleties underlying this observation. Indeed, the different molecular orientation exhibited by the even/odd alkyl chains, and the orientation of the covalently linked carboxylic groups modify the intensity of the magnetic coupling of both octahedral and tetrahedral in-plane sublattices, thus strongly affecting the magnetic properties of the hybrid. These findings offer an outstanding level of tuning in the molecular design of hybrid magnetic materials based on layered hydroxides.