Synthesis Of Coordination Polymers Based On Zwitterionic Ligands And 3d-printing Bespoke Reactionware

Since the beginning of 21st Century,3D printing technology has been developing rapidly,especially in materials processing,bio-medicine,architecture and other fields.3D printing technology can achieve personalized manufacturing from a digital model to a chemical reactor.The application of 3D printing technology to chemical synthesis has a very broad prospect.In this paper,3D printing solvothermal bespoke reactors were designed and manufactured by using polypropylene materials.3D printing reactors are suitable to screen out and optimize the synthetic parameters of new materials rapidly.More over,those reactors can also be applied to explore the multi-step reactions where the chemical composition of the reaction mixture can be changed whilst maintaining the high temperature and pressure environment by just changing the geometry of the reactor itself.12 new coordination polymers were constructed based on 3D printing reactors and two zwitterionic ligands under the solvothermal condition.The obtained materials were characterized and analyzed by means of single crystal X-ray diffraction,powder X-ray diffraction,thermal analysis,FT-IR spectroscopy and elemental analysis.The specific research contents are as follows:1.The monolithic reactors and the compartmentalized reactionware with two partitioned chambers were designed and manufactured by using polypropylene materials to study the synthesis of coordination polymers.Under the solvothermal condition,three new host-guest coordination polymers,compounds 1-3,were synthesized with the precursor ligand N,N’-dicarboxymethyl-4,4’-bipyridinium,connecting ligands(trimesic acid,5-aminoisophthalic acid,2-aminoterephthalic acid)and transition metal ions using the monolithic reactors.Next,we put the reaction mixture of compounds 1-3 into different chambers of the compartmentalized reactionware in pairs,then mixing the reaction systems of two chambers by rotating the reactor at desired time point during the process of solvothermal reaction.Thereafter,the mixed reactor was left undisturbed under the same solvothermal condition until the reaction completed.Finally,four new coordination polymers,compounds 4-7,were successfully obtained.[MV][Co3(aip)4]·4H2O(1)[MV][Co5(btc)4(5H2O)]·2DMF·9H2O·CH3OH(2)[2MV][Cd3(bdc-NH2)4.5Cl(H2O)2]· 8H2O(3)[MV][Cd2Co1.5(btc)3(6H2O)]·6H2O(4)[MV][Cd2Co0.5(btc)2(4H2O)]·OH·5H2O(5)[1/2MV][Cd(btc)(H20)]·2H2O(6)[MV][Cd2(aip)2(bdc-NH2)]·4H20(7)aip = 5-aminoisophthalic acid;btc = trimesic acid;bdc-NH2=2-aminoterephthalic;MV = methyl viologen2.The Two-dimensional coordination polymer(compound 8)and the three-dimensional coordination polymer(compound 9)were obtained based on 4,4’-bis(carboxyphenyl)-bipyridinium and trimesic acid.Three new POM-based coordination polymers,compounds 10-12,were built with polyoxometalates as template and 4,4’-bis(carboxyphenyl)-bipyridinium as connecting ligands by changing the kinds of metal ions.[Co3(bcbp)(btc)2(7H2O)]4H20(8)[Mn3(bcbp)2(btc)2(5H20)]· 8H2O(9)[Ni2(bcbp)2(SiMo12O40)(4H2O)]·2DMF·5H2O(10)[Ni2(bcbp)2(PMo12O40)(4H2O)]·OH·DMF.10H2O(11)[Co2(bcbp)2(PMo12O40)(2H20)]·OH·DMF·9H20(12)btc = trimesic acid...