Magnet-in-ferroelectric crystals exhibiting photomultiferroicity.

Growing crystallographically incommensurate and dissimilar organic materials is fundamentally intriguing but challenging for the prominent cross-correlation phenomenon enabling unique magnetic, electronic, and optical functionalities. Here, we report the growth of molecular layered magnet-in-ferroelectric crystals, demonstrating photomanipulation of interfacial ferroic coupling. The heterocrystals exhibit striking photomagnetization and magnetoelectricity, resulting in photomultiferroic coupling and complete change of their color while inheriting ferroelectricity and magnetism from the parent phases. Under a light illumination, ferromagnetic resonance shifts of 910 Oe are observed in heterocrystals while showing a magnetization change of 0.015 emu/g. In addition, a noticeable magnetization change (8% of magnetization at a 1,000 Oe external field) in the vicinity of ferro-to-paraelectric transition is observed. The mechanistic electric-field-dependent studies suggest the photoinduced ferroelectric field effect responsible for the tailoring of photo-piezo-magnetism. The crystallographic analyses further evidence the lattice coupling of a magnet-in-ferroelectric heterocrystal system.

Biodegradable ferroelectric molecular crystal with large piezoelectric response.

Transient implantable piezoelectric materials are desirable for biosensing, drug delivery, tissue regeneration, and antimicrobial and tumor therapy. For use in the human body, they must show flexibility, biocompatibility, and biodegradability. These requirements are challenging for conventional inorganic piezoelectric oxides and piezoelectric polymers. We discovered high piezoelectricity in a molecular crystal HOCH2(CF2)3CH2OH [2,2,3,3,4,4-hexafluoropentane-1,5-diol (HFPD)] with a large piezoelectric coefficient d33 of ~138 picocoulombs per newton and piezoelectric voltage constant g33 of ~2450 × 10-3 volt-meters per newton under no poling conditions, which also exhibits good biocompatibility toward biological cells and desirable biodegradation and biosafety in physiological environments. HFPD can be composite with polyvinyl alcohol to form flexible piezoelectric films with a d33 of 34.3 picocoulombs per newton. Our material demonstrates the ability for molecular crystals to have attractive piezoelectric properties and should be of interest for applications in transient implantable electromechanical devices.

Supramolecular Metal Halide Complexes for High-Temperature Nonlinear Optical Switches.

Nonlinear optical (NLO) switching materials, which exhibit reversible intensity modulation in response to thermal stimuli, have found extensive applications across diverse fields including sensing, photoelectronics, and photonic applications. While significant progress has been made in solid-state NLO switching materials, these materials typically showcase their highest NLO performance near room temperature. However, this performance drastically deteriorates upon heating, primarily due to the phase transition undergone by the materials from noncentrosymmetric to centrosymmetric phase. Here, we introduce a new class of NLO switching materials, solid-state supramolecular compounds 18-Crown-6 ether@Cu2Cl4·4H2O (1·4H2O), exhibiting reversible and stable NLO switching when subjected to near-infrared (NIR) photoexcitation and/or thermal stimuli. The reversible crystal structure in response to external stimuli is attributed to the presence of a weakly coordinated bridging water molecule facilitated by hydrogen bonding/chelation interactions between the metal halide and crown-ether supramolecules. We observed an exceptionally high second-harmonic generation (SHG) signal under continuous photoexcitation, even at temperatures exceeding 110 °C. In addition, the bridging water molecules within the complex can be released and recaptured in a fully reversible manner, all without requiring excessive energy input. This feature allows for precise control of SHG signal activation and deactivation through structural transformations, resulting in a high-contrast off/on ratio, reaching values in the million-fold range.

Printing conformal and flexible copper networks for multimodal pressure and flow sensing.

Flexible multimodal sensors with ultrasensitive detection capabilities are an indispensable component of wearable electronics and are highly sought-after involving a wide range of signal monitoring such as artificial skin and soft robotics. Here we report a flexible and wireless multimodal sensor using low-temperature additive manufacturing of copper nanoplates on elastic polyurethane substrates for temperature, pressure, and flow monitoring. The positive temperature coefficient and piezoresistive performance of the copper nanoplate network translates to a reliable temperature, steady-state and dynamic pressure/flow sensing for detecting pressures as small as 0.64 Pa with a response time of 130 ms, as well as velocity detection ranging from 2.5-6.8 m s-1. Additionally, by incorporating a printed antenna, it enables a self-powered, battery-free system, offering a wireless readout of printed multimodal sensors with superior real-time sensing performance in conjunction with wearable flexibility.

Proton-controlled molecular ionic ferroelectrics.

Molecular ferroelectric materials consist of organic and inorganic ions held together by hydrogen bonds, electrostatic forces, and van der Waals interactions. However, ionically tailored multifunctionality in molecular ferroelectrics has been a missing component despite of their peculiar stimuli-responsive structure and building blocks. Here we report molecular ionic ferroelectrics exhibiting the coexistence of room-temperature ionic conductivity (6.1 × 10-5 S/cm) and ferroelectricity, which triggers the ionic-coupled ferroelectric properties. Such ionic ferroelectrics with the absorbed water molecules further present the controlled tunability in polarization from 0.68 to 1.39 µC/cm2, thermal conductivity by 13% and electrical resistivity by 86% due to the proton transfer in an ionic lattice under external stimuli. These findings enlighten the development of molecular ionic ferroelectrics towards multifunctionality.

Pressure-controlled magnetism in 2D molecular layers.

Long-range magnetic ordering of two-dimensional crystals can be sensitive to interlayer coupling, enabling the effective control of interlayer magnetism towards voltage switching, spin filtering and transistor applications. With the discovery of two-dimensional atomically thin magnets, a good platform provides us to manipulate interlayer magnetism for the control of magnetic orders. However, a less-known family of two-dimensional magnets possesses a bottom-up assembled molecular lattice and metal-to-ligand intermolecular contacts, which lead to a combination of large magnetic anisotropy and spin-delocalization. Here, we report the pressure-controlled interlayer magnetic coupling of molecular layered compounds via chromium-pyrazine coordination. Room-temperature long-range magnetic ordering exhibits pressure tuning with a coercivity coefficient up to 4 kOe/GPa, while pressure-controlled interlayer magnetism also presents a strong dependence on alkali metal stoichiometry and composition. Two-dimensional molecular interlayers provide a pathway towards pressure-controlled peculiar magnetism through charge redistribution and structural transformation.

Additive manufacturing of eco-friendly building insulation materials by recycling pulp and paper.

Thermal insulation materials by recycling pulp and paper wastes play an important role in environmental sustainability of green buildings. As society is pursuing the goal of zero carbon emissions, it is highly desirable to use eco-friendly materials and manufacturing technologies for building insulation envelopes. Here we report additive manufacturing of flexible and hydrophobic insulation composites from recycled cellulose-based fibers and silica aerogel. The resultant cellulose-aerogel composites exhibit thermal conductivity of 34.68 mW m-1 K-1, mechanical flexibility with a flexural modulus of 429.21 MPa, and superhydrophobicity with water contact angle of 158.72°. Moreover, we present the additive manufacturing process of recycled cellulose aerogel composites, providing enormous potential for high energy efficiency and carbon-sequestration building applications.

Chemical Tuning Meets 2D Molecular Magnets.

2D magnets provoke a surge of interest in large anisotropy in reduced dimensions and are promising for next-generation information technology where dynamic magnetic tuning is essential. Until recently, the crucial metal-organic magnet Cr(pyz)2 ·xLiCl·yTHF with considerable high coercivity and high-temperature magnetic order opens up a new platform to control magnetism in metal-organic materials at room temperature. Here, an in-situ chemical tuning route is reported to realize the controllable transformation of low-temperature magnetic order into room-temperature hard magnetism in Cr(pyz)2 ·xLiCl·yTHF. The chemical tuning via electrochemical lithiation and solvation/desolvation exhibits continuously variable magnetic features from cryogenic magnetism to the room-temperature optimum performance of coercivity (Hc ) of 8500 Oe and energy product of 0.6 MGOe. Such chemically flexible tunability of room-temperature magnetism is ascribed to the different degrees of lithiation and solvation that modify the stoichiometry and Cr-pyrazine coordination framework. Furthermore, the additively manufactured hybrid magnets show air stability and electromagnetic induction, providing potential applications. The findings here suggest chemical tuning as a universal approach to control the anisotropy and magnetism of 2D hybrid magnets at room temperature, promising for data storage, magnetic refrigeration, and spintronics.

Surface-passivated Cu conductors for high-temperature sulfurous environments.

Advanced materials capable of withstanding extreme environments garner extensive interest in the development of next-generation advanced anti-corrosion electronics. Herein, we report that the surface passivation of printed copper conductors imparts corrosion resistance in high-temperature sulfurous environments while maintaining a high electrical conductivity of 4.42 MS m-1 when subjected to a sulfur-containing environment at 350 °C for 12 h. This study provides potential for the development of surface-passivated copper conductors that are resistant to the sulfidizing environments found in several applications of modern technology.

Molecular magneto-ionic proton sensor in solid-state proton battery.

High proton conductivity originated from its small size and the diffusion-free Grotthuss mechanism offers immense promise for proton-based magneto-ionic control of magnetic materials. Despite such promise, the realization of proton magneto-ionics is hampered by the lack of proton-responsive magnets as well as the solid-state sensing method. Here, we report the proton-based magneto-ionics in molecule-based magnet which serves as both solid-state proton battery electrode and radiofrequency sensing medium. The three-dimensional hydrogen-bonding network in such a molecule-based magnet yields a high proton conductivity of 1.6 × 10-3 S cm-1. The three-dimensional printed vascular hydrogel provides the on-demand proton stimulus to enable magneto-ionics, where the Raman spectroscopy shows the redox behavior responsible for the magnetism control. The radiofrequency proton sensor shows high sensitivity in a wide proton concentration range from 10-6 to 1 molar under a low working radiofrequency and magnetic field of 1 GHz and 405 Oe, respectively. The findings shown here demonstrate the promising sensing application of proton-based magneto-ionics.

Releasing chemical energy in spatiallyprogrammed ferroelectrics.

Chemical energy ferroelectrics are generally solid macromolecules showing spontaneous polarization and chemical bonding energy. These materials still suffer drawbacks, including the limited control of energy release rate, and thermal decomposition energy well below total chemical energy. To overcome these drawbacks, we report the integrated molecular ferroelectric and energetic material from machine learning-directed additive manufacturing coupled with the ice-templating assembly. The resultant aligned porous architecture shows a low density of 0.35 g cm-3, polarization-controlled energy release, and an anisotropic thermal conductivity ratio of 15. Thermal analysis suggests that the chlorine radicals react with macromolecules enabling a large exothermic enthalpy of reaction (6180 kJ kg-1). In addition, the estimated detonation velocity of molecular ferroelectrics can be tuned from 6.69 ± 0.21 to 7.79 ± 0.25 km s-1 by switching the polarization state. These results provide a pathway toward spatially programmed energetic ferroelectrics for controlled energy release rates.

Transparent thermal insulation ceramic aerogel materials for solar thermal conversion.

Thermal management in energy-efficient solar thermal energy conversion and transparent windows requires advanced materials with low thermal conductivity and high transparency, such as transparent silica aerogel materials. However, the large scatter domains in porous silica materials would deteriorate their optical transparency. Herein, we report transparent silica aerogels by controlling hydrolyzation and meanwhile silylation modification to enhance the integrity of the microstructure under ambient pressure drying. The transparent silica aerogel materials show a broad-spectrum transparency of 70% from 400 nm and 800 nm, showing promising applications in transparent windows and solar thermal energy conversion systems. The scalability for transparent windows could be achieved with a composite material by incorporating transparent polymeric materials. The solar receiver coupled with a transparent silica aerogel could reach 122 °C within 12 min at a solar irradiance of 1 Sun, ∼200% higher than that in the ambient atmosphere. The engineered structure of the transparent porous silica backbone provides a pathway for solar thermal systems and transparent window applications.

Magnetoelectric interaction in molecular multiferroic nanocomposites.

Incorporation of magnetic and electric orders in a form of multiferroics is an interesting topic in materials science. Making a molecular heterogeneous composite by incorporating the molecular magnet vanadium-chromium Prussian blue analogue (V-Cr PBA) and a molecular ferroelectric imidazolium chloride C3N2H5-ClO4 (ImClO4) provides a pathway towards achieving the room temperature magnetoelectric effect. The change of magnetization of about 6% is shown as a result of applying an electric field (21 kV cm-1) to the composite made of the aforementioned molecular crystals at room temperature. In the ferromagnetic resonance measurement (FMR) under the effect of an applied electric field, a shift of the resonance magnetic field is also observed in the nanocomposites. This work provides a pathway towards molecular multiferroic nanocomposites with magnetoelectric coupling interactions at room temperature.

Dimensional Transformation of Molecular Magnetic Materials.

Two-dimensional (2D) magnetic layered materials have revolutionized size dependent magnetism to manipulate spin-based devices. However, it has been challenging to artificially create 2D magnetic materials from three-dimensional (3D) crystal structures with a variety of material groups. Here, we present the dimensionality manipulation via cation exchange of a 3D Prussian blue analogue [RbMnFe(CN)6] toward a 2D magnetic sheet [(K,Rb)(V,Mn)(Cr,Fe)(CN)6] with the magnetic ordering temperature rising from 12 to 330 K. Such a 2D magnetic sheet achieves crystalline V-Cr coordination in the Prussian blue lattice with pronounced anisotropy and stimuli responsiveness. The pressure dependent magnetic tunability of such 2D networks is predicted using first-principles calculations and demonstrated using the phase transitions of the hydrogel. This previously unobserved phenomenon of dimensional manipulation of a bulk crystal structure provides a rational strategy to expand the diversity and chemical compositions of 2D molecular magnetic material libraries.

Response of Spin to Chiral Orbit and Phonon in Organic Chiral Ferrimagnetic Crystals.

Achiral organic materials show nearly negligible orbit angular momentum, whereas organic ferrimagnets with chirality and reduced electron-lattice scattering could fundamentally bridge the gap between ferromagnetism and antiferromagnetism in the rapidly emerging field of ferrimagnetic spintronics. In this work, we report enantiomeric organic chiral ferrimagnets, where the chirality results from the molecular torsion by propeller-like arrangement of the donor and acceptor molecules. The ferrimagnetism results from the difference in electron-phonon coupling of the donor and acceptor inside the chiral crystals. Because the spin polarization is significantly dependent on the chirality, the magnetization of right-handed organic chiral ferrimagnetic crystals is larger than that of left-handed ones by 300% at 10 K. In addition, the processes of both excitation and recombination are strongly related to spin, phonon, and chiral orbit in these chiral ferrimagnets. Overall, both the organic chiral ferrimagnetism and spin chiroptical activities may substantially enrich the field of organic spintronics.

Manufacturing silica aerogel and cryogel through ambient pressure and freeze drying.

Achieving a mesoporous structure in superinsulation materials is pivotal for guaranteeing a harmonious relationship between low thermal conductivity, high porosity, and low density. Herein, we report silica-based cryogel and aerogel materials by implementing freeze-drying and ambient-pressure-drying processes respectively. The obtained freeze-dried cryogels yield thermal conductivity of 23 mW m-1 K-1, with specific surface area of 369.4 m2 g-1, and porosity of 96.7%, whereas ambient-pressure-dried aerogels exhibit thermal conductivity of 23.6 mW m-1 K-1, specific surface area of 473.8 m2 g-1, and porosity of 97.4%. In addition, the fiber-reinforced nanocomposites obtained via freeze-drying feature a low thermal conductivity (28.0 mW m-1 K-1) and high mechanical properties (∼620 kPa maximum compressive stress and Young's modulus of 715 kPa), coupled with advanced flame-retardant capabilities, while the composite materials from the ambient pressure drying process have thermal conductivity of 28.8 mW m-1 K-1, ∼200 kPa maximum compressive stress and Young's modulus of 612 kPa respectively. The aforementioned results highlight the capabilities of both drying processes for the development of thermal insulation materials for energy-efficient applications.

Molecular copper decomposition ink for printable electronics.

Nanostructured metal materials are the frontrunners of numerous electronic advancements. While realizing such potential, it is indispensable to address their oxidation and stability drawbacks, which are due to their high surface energies. Here, we report printable and air-stable molecular metal ink materials from metal-organic decomposition by using copper ions, including both copper formate and aqueous copper-amine complexes. By complexing copper formate with amines, the decomposition temperature of the printed molecular copper ink can be achieved at 100 °C, while maintaining its electric conductivity. The printed copper conductors exhibit a high electric conductivity of 35 MS m-1 (>50% of bulk copper's electric conductivity at room temperature) and an electromagnetic interference shielding effectiveness of 63 dB. The findings shown here of the molecular decomposition ink are promising for applications in printable electronics.

Tailoring thermal insulation architectures from additive manufacturing.

Tailoring thermal transport by structural parameters could result in mechanically fragile and brittle networks. An indispensable goal is to design hierarchical architecture materials that combine thermal and mechanical properties in a continuous and cohesive network. A promising strategy to create such a hierarchical network targets additive manufacturing of hybrid porous voxels at nanoscale. Here we describe the convergence of agile additive manufacturing of porous hybrid voxels to tailor hierarchically and mechanically tunable objects. In one strategy, the uniformly distributed porous silica voxels, which form the basis for the control of thermal transport, are non-covalently interfaced with polymeric networks, yielding hierarchic super-elastic architectures with thermal insulation properties. Another additive strategy for achieving mechanical strength involves the versatile orthogonal surface hybridization of porous silica voxels retains its low thermal conductivity of 19.1 mW m-1 K-1, flexible compressive recovery strain (85%), and tailored mechanical strength from 71.6 kPa to 1.5 MPa. The printed lightweight high-fidelity objects promise thermal aging mitigation for lithium-ion batteries, providing a thermal management pathway using 3D printed silica objects.

Lithiating magneto-ionics in a rechargeable battery.

Magneto-ionics, real-time ionic control of magnetism in solid-state materials, promise ultralow-power memory, computing, and ultralow-field sensor technologies. The real-time ion intercalation is also the key state-of-charge feature in rechargeable batteries. Here, we report that the reversible lithiation/delithiation in molecular magneto-ionic material, the cathode in a rechargeable lithium-ion battery, accurately monitors its real-time state of charge through a dynamic tunability of magnetic ordering. The electrochemical and magnetic studies confirm that the structural vacancy and hydrogen-bonding networks enable reversible lithiation and delithiation in the magnetic cathode. Coupling with microwave-excited spin wave at a low frequency (0.35 GHz) and a magnetic field of 100 Oe, we reveal a fast and reliable built-in magneto-ionic sensor monitoring state of charge in rechargeable batteries. The findings shown herein promise an integration of molecular magneto-ionic cathode and rechargeable batteries for real-time monitoring of state of charge.

Sprayable copper and copper-zinc nanowires inks for antiviral surface coating.

Copper alloys are known for their high antimicrobial efficacy. Retrofitting high-touch surfaces in public space with solid copper components is expensive and often impractical. Directly coating copper onto these high-touch surfaces can be achieved with hot or cold spray, but the procedure is complicated and requires special equipment. This article reports on the development of sprayable copper and copper-zinc nanowire inks for antiviral surface coating applications. Our results show that copper nanowires inactivate the SARS-CoV-2 virus faster than bulk copper. And a trace amount of zinc addition has a significant effect in enhancing the virucidal effect. More importantly, these nanowire inks are sprayable. They can be easily applied on high-touch surfaces with a spray can. When combined with common chemical disinfectants, the copper-based nanowire ink spray may prolong the disinfecting effect well after application.