Synthesises, Crystal Structures And Properties Of Coordination Polymers Based On Calix[4]arene Tetracarboxylic Acids

Two resorcin[4]arene-based tetracarboxylic acid ligands were synthesized,namely,2,8,14,20-tetra-ethyl-4,10,16,22-tetrakis（（3-carboxybenzyl）oxy）-6,12,18,24-tetra-methoxy-res orcin[4]arene（H4L¹）and 2,8,14,20-tetra-phenyl-4,10,16,22-tetrakis（（3-carboxybenzyl）oxy）-6,12,18,24-tetra-methoxy-resorcin[4]aren e（H4L²）.Based on the two ligands and 1,4,8,11-tetraazacyclotetradecane（cyclam）,five coordination polymers were synthesized by solvothermal methods,namely,[Cu2（L¹）（cyclam）2]·2H₂O（1）,[Ni₂（L¹）（cyclam）₂]·6H₂O（2）,[Cu₂（L²）（cyclam）₂]·6H₂O（3）,[Mn₂（L¹）（H₂O）₃]·2DMF·5H₂O（4）and [（_）2NH₂][Cd3（L¹）（HL¹）（DMF）2（H₂O）3]·DMF·5H₂O（5）.The single crystal structure of these compounds 1-5 was determined by an X-ray single crystal diffractometer.In compounds 1-3,L¹ or L²anions bridge Ni（II）or Cu（II）ions to form a chain structure.In compound 4,two pairs of symmetrically related Mn（II）ions are joined together by carboxyl groups to generate a tetranuclear Mn（II）cluster,which is further linked by L¹ anions to give a one-dimensional chain structure.In compound 5,adjacent Cd（II）ions are bridged by L¹ and HL¹ to yield a three-dimensional framework structure.The compounds were characterized by IR spectra.The solid UV absorption spectra of compounds 1,4 and 5 were measured.The fluorescent sensing property of small organic molecules was studied for 5.