Solvent Control Assembly Three Nuclear Copper Clusters Into Zero D To 3 D Structural Synthesis And Molecular Recognition

In this work, we choose triethanolamine(teaH3), N-methyldiethanolamine(MedeaH2) and4,4’-oxy-bis(benzoate)(oba) as the mixed ligands to explore the different alcoholthermalreactions.Eight novel metal coordination polymers based on such ligands were obtained andfurther characterized by single crystal X-ray diffraction, thermogravimetric analysis and gasadsorption and desorption studies.The eight metal coordination polymers are as follows:Cu3(teaH2)2(oba)2(MeOH)2(1), Cu3(teaH2)2(oba)2(EtOH)2(2), Cu3(teaH2)2(oba)2·(n-PrOH)(3),Cu3(teaH2)2(oba)2(4), Cu3(teaH2)2(oba)2(H2O)2(5), Cu3(MedeaH)2(oba)2(MeOH)2(6),Cu[Cu3(Medea)2(oba)2]·(solvent)x(7), and [Cu3(MedeaH)2(oba)2(H2O)]·(n-PrOH)2(8).The structures of1-8exhibit two types of extensible modes (Mode I for1,2,3,7,8and ModeII for4,5,6) to Cu3SBUs. In1-8, the trinuclear copper SBUs (Cu3) is furnished via thesynergistic coordination of two organic ligands with metal centres. Compounds1and2feature0Dmolecular structures in which two strong hydrogen-bonding interactions extend its molecularcomponents into1D chains by Mode I. Compound3comprises1D chains interspersed by freesolvent molecules whereas compound4consists of2D sheets excluding any solvent molecules.Compound5is also made up of0D molecular structures but uses two classic hydrogen-bondinginteractions to form (4,4) its2D supramolecular connection. Compound6has a similar2Dnetwork to4. Compound7shows an unusual3D microporous framework in which1D chain isfurther assembled by extra CuIIions in Mode I. Compound8provides1D solvated structures withthe voids occupied by lattice solvent molecules. The coordination ability of solvent molecules hasbeen established for the underlying factor behind the different assemblies of compounds1-8.Compounds5and8from alcohol/H2O mixture indicate a behavior of selective coordination to theavailable coordination points of metal centers. The gas sorption property of compound7has alsobeen investigated.This paper study can be draw a conclusion that the coordination order isH2O>MeOH>EtOH>PrOH.Varying the solvothermal reactions from MeOH to PrOH and then tothe alcohol/H2O mixture results in a series of very beautiful coordination polymers. Theirstructural evolutions are involved inthe remarkable solvent-dependent assembly of Cu3SUBs.This contribution deals with two important aspects:1) the collaborative use of polyalcohol amines(teaH3: triethanolamine and MedeaH2: N-methyldiethanolamine) and4,4’-oxy-bis(benzoate)(oba)to guarantee the repetition for the consistent Cu3SUBs;2) the solvent controllability over theircrystal structures is heavily relative to solvent coordination ability.