Preparation Of Ordered Heterostructures Based On Macroscopic Supramolecular Assembly By Flexible Coating Strategy

Macroscopic supramolecular assembly(MSA)is a rising method to fabricate supramolecular bulk materials using building blocks above 10 micrometers through the multivalent noncovalent interaction.It is a newly facile methodology to fabricate bulk supramolecular materials from the bottom up.Macroscopic supramolecular assembly is easily achieved in the low elastic modulus material system,but it is difficult for high-modulus materials to achieve assembly.The reason is that many high-modulus building blocks have poor surface deformability and differentiated functional group distributions,making it difficult for most functional groups to reach the intermolecular force range.Therefore,macroscopic supramolecular assembly research is mostly limited to low modulus materials,and the assembly of highly elastic modulus materials has become a bottleneck restricting the development in this field.In addition,the assembly process is usually a random collision condition,and the resulting assemblies are often low in controllability and order,which hinders the large-scale preparation of bulk phase supramolecular materials and its wide application.Herein,to achieve the assembly of high elastic modulus building blocks,we built flexible spacer coatings on the surface by chemically anchoring hydrogel coatings or introducing flexible polyelectrolyte multilayer films.Further,we have achieved a controlled and ordered heterogeneous assembly,through the anisotropic modification of the hydrogel coating and the precise positioning assisted by the magnetic field.The main conclusions are as follows:(1)We have proposed a strategy of covalently connecting a low-modulus supramolecular hydrogel coating on the building blocks as a new type of flexible spacing coating,and realized the macroscopic supramolecular assembly of a variety of high-modulus building blocks between metals,quartz,plastic.(2)Through the anisotropic modification of the supramolecular hydrogel coating on the surface of various building blocks,we realized the programmable controllable assembly of the heterogeneous structure with the designed shape.(3)We accurately prepare target 3D heterogeneous structures with complex shapes by using polyelectrolyte multilayer PEI/PAA film as a flexible spacing coating combined with 3D magnetic manipulation technology to accurately position the component,which solves the effective compounding of the various materials in three dimensions.