Molecular Connectors Boosting the Performance of MoS2 Cathodes in Zinc-Ion Batteries.

Zinc-ion batteries (ZIBs) are promising energy storage systems due to high energy density, low-cost, and abundant availability of zinc as a raw material. However, the greatest challenge in ZIBs research is lack of suitable cathode materials that can reversibly intercalate Zn2+ ions. 2D layered materials, especially MoS2 -based, attract tremendous interest due to large surface area and ability to intercalate/deintercalate ions. Unfortunately, pristine MoS2 obtained by traditional protocols such as chemical exfoliation or hydrothermal/solvothermal methods exhibits limited electronic conductivity and poor chemical stability upon charge/discharge cycling. Here, a novel molecular strategy to boost the electrochemical performance of MoS2 cathode materials for aqueous ZIBs is reported. The use of dithiolated conjugated molecular pillars, that is, 4,4'-biphenyldithiols, enables to heal defects and crosslink the MoS2 nanosheets, yielding covalently bridged networks (MoS2 -SH2) with improved ionic and electronic conductivity and electrochemical performance. In particular, MoS2 -SH2 electrodes display high specific capacity of 271.3 mAh g-1 at 0.1 A g-1 , high energy density of 279 Wh kg-1 , and high power density of 12.3 kW kg-1 . With its outstanding rate capability (capacity of 148.1 mAh g-1 at 10 A g-1 ) and stability (capacity of 179 mAh g-1 after 1000 cycles), MoS2 -SH2 electrodes outperform other MoS2 -based electrodes in ZIBs.

High Selectivity and Sensitivity in Chemiresistive Sensing of Co(II) Ions with Liquid-Phase Exfoliated Functionalized MoS2 : A Supramolecular Approach.

Chemical sensing of water contamination by heavy metal ions is key as it represents a most severe environmental problem. Liquid-phase exfoliated two-dimensional (2D) transition metal dichalcogenides (TMDs) are suitable candidates for chemical sensing thanks to their high surface-to-volume ratio, sensitivity, unique electrical characteristics, and scalability. However, TMDs lack selectivity due to nonspecific analyte-nanosheet interactions. To overcome this drawback, defect engineering enables controlled functionalization of 2D TMDs. Here, ultrasensitive and selective sensors of cobalt(II) ions via the covalent functionalization of defect-rich MoS2 flakes with a specific receptor, 2,2':6',2″-terpyridine-4'-thiol is developed. A continuous network is assembled by healing of MoS2 sulfur vacancies in a tailored microfluidic approach, enabling high control over the assembly of thin and large hybrid films. The Co2+ cations complexation represents a powerful gauge for low concentrations of cationic species which can be best monitored in a chemiresisitive ion sensor, featuring a 1 pm limit of detection, sensing in a broad concentration range (1 pm - 1 µm) and sensitivity as high as 0.308 ± 0.010 lg([Co2+ ])-1 combined with a high selectivity towards Co2+ over K+ , Ca2+ , Mn2+ , Cu2+ , Cr3+ , and Fe3+ cations. This supramolecular approach based on highly specific recognition can be adapted for sensing other analytes through specific ad-hoc receptors.

Controlling the Formation of Electroactive Graphene-Based Cementitious Composites: Towards Structural Health Monitoring of Civil Structures.

The development of composites combining multiple components each one imparting a specific function to the ensemble is highly sought after for disruptive applications in chemistry and materials science, with a particular importance for the realization of smart structures. Here, we report on the development of an unprecedented multifunctional cementitious composite incorporating reduced graphene oxide (rGO). By design, this material features significantly enhanced electrical properties while retaining the excellent cement's hydration and microstructure. The multiscale investigation on the chemical and physical properties of the dispersion made it possible to establish an efficient preparation protocol for rGO aqueous dispersion as well as rGO-based cementitious composites using a commercial poly(carboxylate ether)-based superplasticizer. The conduction mechanisms within the matrix of rGO containing mortars were unraveled by electrochemical impedance spectroscopy revealing conductive paths originating from bulk cement matrix and rGO nanosheets in composites with rGO loadings as low as 0.075 wt. %. For this rGO loading, we observed the reduction of the resistivity of bulk cement mortar layers from 18.3 MΩ cm to 2.8 MΩ cm. Moreover, the addition of 0.2 wt. % of rGO resulted in the formation of rGO conductive paths with the resistivity of 51.1 kΩ cm. These findings represent a major step forward towards the practical application of graphene-based materials in structural health monitoring of concrete structures.

Dynamic Cages-Towards Nanostructured Smart Materials.

The interest in capsular assemblies such as dynamic organic and coordination cages has blossomed over the last decade. Given their chemical and structural variability, these systems have found applications in diverse fields of research, including energy conversion and storage, catalysis, separation, molecular recognition, and live-cell imaging. In the exploration of the potential of these discrete architectures, they are increasingly being employed in the formation of more complex systems and smart materials. This Review highlights the most promising pathways to overcome common drawbacks of cage systems (stability, recovery) and discusses the most promising strategies for their hybridization with systems featuring various dimensionalities. Following the description of the most recent advances in the fabrication of zero to three-dimensional cage-based systems, this Review will provide the reader with the structure-dependent relationship between the employed cages and the properties of the materials.

Supramolecular Engineering of Cathode Materials for Aqueous Zinc-ion Energy Storage Devices: Novel Benzothiadiazole Functionalized Two-Dimensional Olefin-Linked COFs.

Two-dimensional covalent organic frameworks (COFs) have emerged as promising materials for energy storage applications exhibiting enhanced electrochemical performance. While most of the reported organic cathode materials for zinc-ion batteries use carbonyl groups as electrochemically-active sites, their high hydrophilicity in aqueous electrolytes represents a critical drawback. Herein, we report a novel and structurally robust olefin-linked COF-TMT-BT synthesized via the aldol condensation between 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4'-(benzothiadiazole-4,7-diyl)dibenzaldehyde (BT), where benzothiadiazole units are explored as novel electrochemically-active groups. Our COF-TMT-BT exhibits an outstanding Zn2+ storage capability, delivering a state-of-the-art capacity of 283.5 mAh g-1 at 0.1 A g-1 . Computational and experimental analyses reveal that the charge-storage mechanism in COF-TMT-BT electrodes is based on the supramolecularly engineered and reversible Zn2+ coordination by the benzothiadiazole units.

New Anderson-Based Polyoxometalate Covalent Organic Frameworks as Electrodes for Energy Storage Boosted Through Keto-Enol Tautomerization.

The unique electrochemical properties of polyoxometalates (POMs) render them ideal components for the fabrication of next-generation high-performance energy storage systems. However, their practical applications have been hindered by their high solubility in common electrolytes. This problem can be overcome by the effective hybridization of POMs with other materials. Here we present the design and synthesis of two novel polyoxometalate-covalent organic frameworks (POCOF) via one-pot solvothermal strategy between an amino-functionalized Anderson-type POM and a trialdehyde-based building unit. We show that structural and functional complexity can be enriched by adding hydroxyl groups in the 2,4,6 position to the benzene-1,3,5-tricarbaldehyde allowing to exploit for the first time in POCOFs the keto-enol tautomerization as additional feature to impart greater chemical stability to the COFs and enhanced properties leading to large specific surface area (347 m2 /g) and superior electrochemical performance of the POCOF-1 electrodes, when compared with POCOF-2 electrodes that possess only imine-type linkage and with pristine POM electrodes. Specifically, POCOF-1 electrodes display remarkable specific, areal, and volumetric capacitance (125 F/g, 248 mF/cm2 and 41.9 mF/cm3 , respectively) at a current density of 0.5 A/g, a maximum energy density (56.2 Wh/kg), a maximum power density (3.7 kW/kg) and an outstanding cyclability (90 % capacitance retention after 5000 cycles).

Solution-Processed Graphene-Nanographene van der Waals Heterostructures for Photodetectors with Efficient and Ultralong Charge Separation.

Sensitization of graphene with inorganic semiconducting nanostructures has been demonstrated as a powerful strategy to boost its optoelectronic performance. However, the limited tunability of optical properties and toxicity of metal cations in the inorganic sensitizers prohibits their widespread applications, and the in-depth understanding of the essential interfacial charge-transfer process within such hybrid systems remains elusive. Here, we design and develop high-quality nanographene (NG) dispersions with a large-scale production using high-shear mixing exfoliation. The physisorption of these NG molecules onto graphene gives rise to the formation of graphene-NG van der Waals heterostructures (VDWHs), characterized by strong interlayer coupling through π-π interactions. As a proof of concept, photodetectors fabricated on the basis of such VDWHs show ultrahigh responsivity up to 4.5 × 107 A/W and a specific detectivity reaching 4.6 × 1013 Jones, being competitive with the highest values obtained for graphene-based photodetectors. The outstanding device characteristics are attributed to the efficient transfer of photogenerated holes from NGs to graphene and the long-lived charge separation at graphene-NG interfaces (beyond 1 ns), as elucidated by ultrafast terahertz (THz) spectroscopy. These results demonstrate the great potential of such graphene-NG VDWHs as prototypical building blocks for high-performance, low-toxicity optoelectronics.

Highly Sensitive Strain Sensors Based on Molecules-Gold Nanoparticles Networks for High-Resolution Human Pulse Analysis.

High-performance flexible strain sensors are key components for the next generation of wearable health monitoring devices. Here, the authors have fabricated a novel strain sensor based on gold nanoparticles (AuNPs) interconnected by flexible and responsive molecular linkers. The combination of conductive AuNPs (25 nm in diameter) with tetra(ethylene glycol) dithiol (SH-TEG-SH) linkers yields a covalent 3D network which can be directly deposited onto prepatterned flexible supports exposing interdigitated Au electrodes. The electrically insulating nature of the linkers effectively defines the tunneling modulated charge transfer through the AuNPs network. When compressive/tensile strain is applied, the molecular linkers adopt a compressed/stretched conformation thus decreasing/increasing the interparticle distance, ultimately yielding an exponential increase/decrease of the tunneling current when voltage is applied. The strain sensor displays state-of-the-art performances including a highly sensitive response to both tensile and compressive strain, as quantified by a high gauge factor (GF≈126) combined with other superior sensing properties like high flexibility, short response time (16.1 ms), and good robustness (>2000 cycles). Finally, the applicability of the device for health monitoring is demonstrated: high-resolution artery pulse waves are acquired by placing the strain sensor onto the skin allowing the extraction of important physical parameters for human-health assessment.

Self-Assembly of Functionalized Lipophilic Guanosines into Cation-Free Stacked Guanine-Quartets.

The hierarchical self-assembly of various lipophilic guanosines exposing either a phenyl or a ferrocenyl group in the C(8) position was investigated. In a solution, all the derivatives were found to self-assemble primarily into isolated guanine (G)-quartets. In spite of the apparent similar bulkiness of the two substituents, most of the derivatives form disordered structures in the solid state, whereas a specific 8-phenyl derivative self-assembles into an unprecedented, cation-free stacked G-quartet architecture.

Functionalized 4,4'-Bipyridines: Synthesis and 2D Organization on Highly Oriented Pyrolytic Graphite.

Commercial 4,4'-bipyridine is a popular scaffold that is primarily employed as a linker in 3D self-assembled architectures such as metallo-organic frameworks or as a connector in 2D networks. The introduction of alkyl substituents on the bipyridine skeleton is instrumental when 4,4'-bipyridines are used as linkers to form 2D self-assembled patterns on surfaces. Here, several synthetic strategies to access 4,4'-bipyridines functionalized at various positions are described. These easily scalable reactions have been used to introduce a range of alkyl substituents at positions 2 and 2' or 3 and 3' and at positions 2,2' and 6,6' in the case of tetra-functionalization. Scanning tunneling microscopy studies of molecular monolayers physisorbed at the graphite-solution interface revealed different supramolecular patterns whose motifs are primarily dictated by the nature and position of the alkyl chains.

Chemical Conversion and Locking of the Imine Linkage: Enhancing the Functionality of Covalent Organic Frameworks.

Imine-based covalent organic frameworks (COFs) are a widely studied class of functional, crystalline, and porous nanostructures which combine a relatively facile crystallization with tuneable compositions and porosities. However, the imine linkage constitutes an intrinsic limitation due to its reduced stability in harsh chemical conditions and its unsuitability for in-plane π-conjugation in COFs. Urgent solutions are therefore required in order to exploit the full potential of these materials, thereby enabling their technological application in electronics, sensing, and energy storage devices. In this context, the advent of a new generation of linkages derived from the chemical conversion and locking of the imine bond represents a cornerstone for the synthesis of new COFs. A marked increase in the framework robustness is in fact often combined with the incorporation of novel functionalities including, for some of these reactions, an extension of the in-plane π-conjugation. This Minireview describes the most enlightening examples of one-pot reactions and post-synthetic modifications towards the chemical locking of the imine bond in COFs.

Molecular Springs: Integration of Complex Dynamic Architectures into Functional Devices.

Molecular/supramolecular springs are artificial nanoscale objects possessing well-defined structures and tunable physicochemical properties. Like a macroscopic spring, supramolecular springs are capable of switching their nanoscale conformation as a response to external stimuli by undergoing mechanical spring-like motions. This dynamic action offers intriguing opportunities for engineering molecular nanomachines by translating the stimuli-responsive nanoscopic motions into macroscopic work. These nanoscopic objects are reversible dynamic multifunctional architectures which can express a variety of novel properties and behave as adaptive nanoscopic systems. In this Minireview, we focus on the design and structure-property relationships of supramolecular springs and their (self-)assembly as a prerequisite towards the generation of novel dynamic materials featuring controlled movements to be readily integrated into macroscopic devices for applications in sensing, robotics, and the internet of things.

Synthesis of Robust MOFs@COFs Porous Hybrid Materials via an Aza-Diels-Alder Reaction: Towards High-Performance Supercapacitor Materials.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted enormous attention in recent years. Recently, MOF@COF are emerging as hybrid architectures combining the unique features of the individual components to enable the generation of materials displaying novel physicochemical properties. Herein we report an unprecedented use of aza-Diels-Alder cycloaddition reaction as post-synthetic modification of MOF@COF-LZU1, to generate aza-MOFs@COFs hybrid porous materials with extended π-delocalization. A a proof-of-concept, the obtained aza-MOFs@COFs is used as electrode in supercapacitors displaying specific capacitance of 20.35 µF cm-2 and high volumetric energy density of 1.16 F cm-3 . Our approach of post-synthetic modification of MOFs@COFs hybrids implement rational design for the synthesis of functional porous materials and expands the plethora of promising application of MOFs@COFs hybrid porous materials in energy storage applications.

Graphene Oxide Hybrid with Sulfur-Nitrogen Polymer for High-Performance Pseudocapacitors.

Toward the introduction of fast faradaic pseudocapacitive behavior and the increase of the specific capacitance of carbon-based electrodes, we covalently functionalized graphene oxide with a redox active thiourea-formaldehyde polymer, yielding a multifunctional hybrid system. The multiscale physical and chemical characterization of the novel 3-dimensional hybrid revealed high material porosity with high specific surface area (402 m2 g-1) and homogeneous element distribution. The presence of multiple functional groups comprising sulfur, nitrogen, and oxygen provide additional contribution of Faradaic redox reaction in supercapacity performance, leading to a high effective electrochemical pseudocapacitance. Significantly, our graphene-based 3-dimensional thiourea-formaldehyde hybrid exhibited specific capacitance as high as 400 F g-1, areal capacitance of 160 mF cm-2, and an energy density of 11.1 mWh cm-3 at scan rate of 1 mV s-1 with great capacitance retention (100%) after 5000 cycles at scan rate of 100 mV s-1.

Chemical sensing with 2D materials.

During the last decade, two-dimensional materials (2DMs) have attracted great attention due to their unique chemical and physical properties, which make them appealing platforms for diverse applications in opto-electronic devices, energy generation and storage, and sensing. Among their various extraordinary properties, 2DMs possess high surface area-to-volume ratios and ultra-high surface sensitivity to the environment, which are key characteristics for applications in chemical sensing. Furthermore, 2DMs' superior electrical and optical properties, combined with their excellent mechanical characteristics such as robustness and flexibility, make these materials ideal components for the fabrication of a new generation of high-performance chemical sensors. Depending on the specific device, 2DMs can be tailored to interact with various chemical species at the non-covalent level, making them powerful platforms for fabricating devices exhibiting a high sensitivity towards detection of various analytes including gases, ions and small biomolecules. Here, we will review the most enlightening recent advances in the field of chemical sensors based on atomically-thin 2DMs and we will discuss the opportunities and the challenges towards the realization of novel hybrid materials and sensing devices.

Chemical Synthesis at Surfaces with Atomic Precision: Taming Complexity and Perfection.

Scanning probe microscopy (SPM) is a powerful tool to study the structure and dynamics of molecules at surfaces and interfaces as well as to precisely manipulate atoms and molecules by applying an external force, by inelastic electron tunneling, or by means of an electric field. The rapid development of these SPM manipulation modes made it possible to achieve fine-control over fundamental processes in the physics of interfaces as well as chemical reactivity, such as adsorption, diffusion, bond formation, and bond dissociation with precision at the single atom/molecule level. Their controlled use for the fabrication of atomic-scale structures and synthesis of new, perhaps uncommon, molecules with programmed properties are reviewed. Opportunities and challenges towards the development of complex chemical systems are discussed, by analyzing potential future impacts in nanoscience and nanotechnology.

Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self-Assembly at Surfaces of Multifunctional Systems.

Salophens and Salens are Schiff bases generated through the condensation of two equivalents of salicylaldehyde with either 1,2-phenylenediamines or aliphatic diamines, respectively. Both ligands have been extensively exploited as key building blocks in coordination chemistry and catalysis. In particular, their metal complexes have been widely used for various catalytical transformations with high yield and selectivity. Through the modification of the phenol unit it is possible to tune the steric hindrance and electronic properties of Salophen and Salen. The introduction of long aliphatic chains in salicylaldehydes can be used to promote their self-assembly into ordered supramolecular structures on solid surfaces. Herein, we report a novel method towards the facile synthesis of robust and air-stable [Al(Salophen)] derivatives capable of undergoing spontaneous self-assembly at the graphite/solution interface forming highly-ordered nanopatterns. The new synthetic approach relies on the use of [MeAlIII (Salophen)] as a building unit to introduce, via a simple acid/base reaction with functionalized acidic phenol derivatives, selected frameworks integrating multiple functions for efficient surface decoration. STM imaging at the solid/liquid interface made it possible to monitor the formation of ordered supramolecular structures. In addition, the redox properties of the Salophen derivatives functionalized with ferrocene units in solution and on surface were unraveled by cyclic voltammetry. The use of a five-coordinate aluminum alkyl Salophen precursor enables the tailoring of new Salophen molecules capable of undergoing controlled self-assembly on HOPG, and thereby it can be exploited to introduce multiple functionalities with subnanometer precision at surfaces, ultimately forming ordered functional patterns.

Self-Assembled Two-Dimensional Supramolecular Networks Characterized by Scanning Tunneling Microscopy and Spectroscopy in Air and under Vacuum.

We combine ambient (air) and ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) and spectroscopy (STS) investigations together with density functional theory (DFT) calculations to gain a subnanometer insight into the structure and dynamic of two-dimensional (2D) surface-supported molecular networks. The planar tetraferrocene-porphyrin molecules employed in this study undergo spontaneous self-assembly via the formation of hydrogen bonded networks at the gold substrate-solution interface. To mimic liquid phase ambient deposition conditions, film formation was accomplished in UHV by electro-spraying a solution of the molecule in chloroform onto an Au(111) substrate, thereby providing access to the full spectroscopic capabilities of STM that can be hardly attained under ambient conditions. We show that molecular assembly on Au (111) is identical in films prepared under the two different conditions, and in good agreement with the theoretical predictions. However, we observe the contrast found for a given STM bias condition to be different in ambient and UHV conditions despite the similarity of the structures, and we propose possible origins of the different imaging contrast. This approach could be valuable for the thorough characterization of surface systems that involve large molecules and are prepared mainly in ambient conditions.

Light-Induced Contraction/Expansion of 1D Photoswitchable Metallopolymer Monitored at the Solid-Liquid Interface.

The use of a bottom-up approach to the fabrication of nanopatterned functional surfaces, which are capable to respond to external stimuli, is of great current interest. Herein, the preparation of light-responsive, linear supramolecular metallopolymers constituted by the ideally infinite repetition of a ditopic ligand bearing an azoaryl moiety and Co(II) coordination nodes is described. The supramolecular polymerization process is followed by optical spectroscopy in dimethylformamide solution. Noteworthy, a submolecularly resolved scanning tunneling microscopy (STM) study of the in situ reversible trans-to-cis photoisomerization of a photoswitchable metallopolymer that self-assembles into 2D crystalline patterns onto a highly oriented pyrolytic graphite surface is achieved for the first time. The STM analysis of the nanopatterned surfaces is corroborated by modeling the physisorbed species onto a graphene slab before and after irradiation by means of density functional theory calculation. Significantly, switching of the monolayers consisting of supramolecular Co(II) metallopolymer bearing trans-azoaryl units to a novel pattern based on cis isomers can be triggered by UV light and reversed back to the trans conformer by using visible light, thereby restoring the trans-based supramolecular 2D packing. These findings represent a step forward toward the design and preparation of photoresponsive "smart" surfaces organized with an atomic precision.

Self-assembly of Natural and Unnatural Nucleobases at Surfaces and Interfaces.

The self-assembly of small organic molecules interacting via non-covalent forces is a viable approach towards the construction of highly ordered nanostructured materials. Among various molecular components, natural and unnatural nucleobases can undergo non-covalent self-association to form supramolecular architectures with ad hoc structural motifs. Such structures, when decorated with appropriate electrically/optically active units, can be used as scaffolds to locate such units in pre-determined positions in 2D on a surface, thereby paving the way towards a wide range of applications, e.g., in optoelectronics. This review discusses some of the basic concepts of the supramolecular engineering of natural and unnatural nucleobases and derivatives thereof as well as self-assembly processes on conductive solid substrates, as investigated by scanning tunnelling microscopy in ultra-high vacuum and at the solid/liquid interface. By unravelling the structure and dynamics of these self-assembled architectures with a sub-nanometer resolution, a greater control over the formation of increasingly sophisticated functional systems is achieved. The ability to understand and predict how nucleobases interact, both among themselves as well as with other molecules, is extremely important, since it provides access to ever more complex DNA- and RNA-based nanostructures and nanomaterials as key components in nanomechanical devices.