Solvent Dependent Assembly,Structural Diversity and Topology Analysis in Two Novel Ni Coordination Polymers

Solvent dependent assembly obtained two novel Ni coordination polymers with H_2 tbtpa and flexible 1,2-bix ligand（H_2tbtpa = tetrabromoterephthalic acid and 1,2-bix = 1,2-bis（imidazol-1-ylmethyl）benzene）,formulated as [Ni_（0.5）（tbtpa）_（0.5）（1,2-bix）·（H_2O）]_n（1） and [Ni（tbtpa）（1,2-bix）（H_2O）_2]_n（2）.They have been structurally characterized by single-crystal and powder X-ray diffraction,elemental analysis,FT-IR spectra and TGA.Compound 1 crystalizes in triclinic,space group P1 with a = 9.0276（4）,b = 10.0012（6）,c = 11.4955（5） A,α = 69.121（5）,β = 76.398（4）,γ = 89.668（4）o,C_（36）H_（32）Br_4 Ni N_8O_6,Mr = 1051.04,V = 939.05（8） A^3,Z = 1,Dc = 1.859 g·cm^-3,μ = 6.222 mm^-1,F（000） = 520,8.502≤2θ≤134.16°,λ（Cu Kα） = 1.54184 A,T = 294（6） K,the final R = 0.0750,w R = 0.1988 and S = 1.033.Compound 2 crystalizes in triclinic,space group P1 with a = 11.1257（7）,b = 11.5062（6）,c = 12.3529（4） A,α = 88.861（3）,β = 84.572（4）,γ = 64.235（6）o,C_（22）H_（18）Br_4 Ni N_4O_6,Mr = 812.75,V = 1417.36（1） A^3,Z = 2,Dc = 1.904 g·cm^-3,μ = 7.968 mm^-1,F（000） = 788,7.2≤2θ≤134.1°,λ（Cu Kα） = 1.54184 A,T = 294（6） K,the final R = 0.0414,w R = 0.0865 and S = 1.025.1 shows a two-dimensional（4,4）-sql topology and 2 manifests a three-dimensional 6~58 Cd SO_4 topology coordination polymer network.

Stepwise assembly of heterometallic 3d–4f chain exhibiting slow magnetic relaxation

The self-assembly of polyalcohol ligand 1,1,1-tris（hydroxymethyl）ethane with Dy（NO3）3· 6H2 O and Cr3O-Bzo-t-Bu precursor in the presence of triethylamine step-by-step generated a heterometallic 3d–4f chain. Magnetic investigation of the complex indicates typical slow relaxation of the magnetization at low temperature.

Reprogrammable 3D Mesostructures Through Compressive Buckling of Thin Films with Prestrained Shape Memory Polymer

The mechanically guided assembly that relies on the compressive buckling of strate- gically patterned 2D thin films represents a robust route to complex 3D mesostructures in advanced materials and even functional micro-devices. Based on this approach, formation of complex 3D configurations with suspended curvy features or hierarchical geometries remains a challenge. In this paper, we incorporate the prestrained shape memory polymer in the 2D precur- sor design to enable local rolling deformations after the mechanical assembly through compressive buckling. A theoretical model captures quantitatively the effect of key design parameters on local rolling deformations. The combination of precisely controlled global buckling and local rolling expands substantially the range of accessible 3D configurations. The combined experimental and theoretical studies over a dozen of examples demonstrate the utility of the proposed strategy in achieving complex reprogrammable 3D mesostructures.

A bio-inspired 3D metamaterials with chirality and anti-chirality topology fabricated by 4D printing

Artificial architected metamaterials equipped with unique mechanical and physical properties that are naturally inaccessible can be obtained by rational design.In this work,the innovative three-dimensional(3D)chiral and anti-chiral metamaterials are developed referring to the face-rotating polyhedral(FRP)structure present in the virus.Through assembling planar triangular units into the regular octahedron cells,several typical forms of chiral and anti-chiral metamaterials can be obtained by different assembly methods.By changing the topology parameters,the Poisson’s ratio can be adjusted between[0,2.8].The metamaterials are fabricated by 3D printing utilizing shape memory polymer,and the mechanical properties are analyzed via Finite Element Analysis(FEA)and experiments,including Young’s modulus,Poisson’s ratio,and tension-twist coupling behavior.In addition,target metamaterial with specific local deformation behavior is obtained by programmatic calculations and distributions to meet special requirements or achieve unique applications.The shape memory property endows the mechanical metamaterials with more potential applications.

Morphable three-dimensional electronic mesofliers capable of on-demand unfolding

Development of miniaturized three-dimensional(3 D)fliers with integrated functional components has important implications to a diverse range of engineering areas.Among the various active and passive miniaturized 3 D fliers reported previously,a class of 3 D electronic fliers inspired by wind-dispersed seeds show promising potentials,owing to the lightweight and noiseless features,aside from the stable rotational fall associated with a low falling velocity.While on-demand shape-morphing capabilities are essential for those 3 D electronic fliers,the realization of such miniaturized systems remains very challenging,due to the lack of fast-response 3 D actuators that can be seamlessly integrated with 3 D electronic fliers.Here we develop a type of morphable3 D mesofliers with shape memory polymer(SMP)-based electrothermal actuators,capable of large degree of actuation deformations,with a fast response(e.g.,~1 s).Integration of functional components,including sensors,controllers,and chip batteries,enables development of intelligent 3 D mesoflier systems that can achieve the on-demand unfolding,triggered by the processing of real-time sensed information(e.g.,acceleration and humidity data).Such intelligent electronic mesofliers are capable of both the low-air-drag rising and the low-velocity falling,and thereby,can be used to measure the humidity fields in a wide 3 D space by simple hand throwing,according to our demonstrations.The developed electronic mesofliers can also be integrated with other types of physical/chemical sensors for uses in different application scenarios.

Multi-functional stimuli-responsive biomimetic flower assembled from CLCE and MOF-based pedals

Simulating the structures and behaviors of living organisms are of great significance to develop novel multi-functional intelligent devices. However, the development of biomimetic devices with complex deformable structures and synergistic properties is still on the way. Herein, we propose a simple and effective approach to create the multi-functional stimuli-responsive biomimetic devices with independently pre-programmable colorful visual patterns, complex geometries and morphable modes. The metal organic framework(MOF)-based composite film acts as a rigidity actuation substrate to support and mechanically guide the spatial configuration of the soft chiral nematic liquid crystal elastomer(CLCE) sheet. We can directly program the structural color of the CLCE sheet by adjusting the thickness distribution without tedious chemical modification. By using this coordination strategy, we fabricate an artificial flower, which exhibits a synergistic effect of both shape transformation and color change like paeonia ‘Coral Sunset’at different flowering stages, and can even perform different flowering behaviors by bending, twisting and curling petals. The assembled bionic flower is innovatively demonstrated to respond to local stimuli of humidity, heat or ultraviolet irradiation. Therefore, the spatial assembly of CLCE combined with functional MOF materials has a wide range of potential application in multi-functional integrated artificial systems.

Probability-Based Analyses of the Snap-Through in Cage-Shaped Mesostructures Under Out-of-Plane Compressions

Three-dimensional(3D)mesostructures with distinct compressive deformation behaviors and tunable mechanical responses have gained increasing interest in recent years.3D cage-shaped mesostructures are representative framework structures widely exploited in 3D flexible electronics,owing to their unique cellular geometry and unusual mechanical responses.The snap-through behavior of cage-shaped mesostructures could potentially result in the performance degradation of electronics,while it could also be harnessed to design reconfigurable electronics.Due to the complicated deformation modes and random characteristics in experiments,the snap-through behavior of cage-shaped mesostructures remains largely unexplored,espe-cially in terms of probability-based analyses.In this work,we present a systematic study on the configuration evolution and snap-through of 3D cage-shaped mesostructures under out-of-plane compressions.Experimental and computational studies show the existence of two distinct deformation modes associated with the snap-through,which is controlled by the energy barrier based on the energetic analyses.Phase diagrams of the deformation modes decode how key geometric parameters and assembly strain affect the snap-through.Compressive experiments based on periodic arrays(10 × 10)of mesostructures provided a large amount of deformation data,allowing for statistical analyses of the snap-through behavior.These results provide new insights and useful guidelines for the design of 3D reconfigurable devices and multistable metamaterials based on 3D cage-shaped mesostructures.

Wrinkling modes of graphene oxide assembled on curved surfaces

Assembling two-dimensional(2D)sheets into macroscopic three-dimensional(3D)forms has created a promising material family with rich functionalities.Multiscale wrinkles are intrinsic features of 2D sheets in their 3D assembles.Therefore,the precise wrinkling modulation optimizes the transition of outstanding properties of 2D sheets to expected performances of assembled materials and dominates their fabrication process.The wrinkling evolution of 2D sheets assembling onto flat surfaces has been extensively understood,however,the wrinkling behaviors on the more generally curved surface still remain unclear.Here,we investigate the wrinkling behaviors of graphene oxide sheets assembled onto curved surfaces and reveal the selection rule of wrinkling modes that determined by the curvature mismatch between 2D sheets and target surfaces.We uncover that three wrinkling modes including isotropic cracked land,labyrinth,and anisotropic curtain phases,respectively emerge on flat,spherical,and cylindrical surfaces.A favorable description paradigm is offered to quantitatively measure the complex wrinkling patterns and assess the curvature mismatch constraint underlying the wrinkling mode selection.This research provides a general and quantitative description framework of wrinkling modulation of 2D materials such as high performance graphene fibers,and guides the precise fabrication of particles and functional coatings.