Syntheses And Properties Of Coordination Compounds Constructed From Resorcin[4] Arene Derivatives

In this paper,five kinds of resorcin[4]arene derivatives were used as ligands and a series of complexes with diverse structures and potential applications were successfully synthesized.The single crystal X-ray diffractometer,infrared spectra,and powder X-ray diffraction spectra were used for characterization.In addition,luminescence properties,ion exchange and catalysis of some complexes were also investigated.1.We present a new family of Ag（I）complexes bearing calixarene-based tetraethynide ligands,namely[Ag₁₂（L1）₂·（CH₃CN）₄·（NO₃）₄]·2H₂O（1）,[Ag₄L1·（AgCF₃CO₂）₄·（CH₃OH）]（2）,[Ag₄L2·（AgCF₃CO₂）₄]·H₂O（3）and[Ag₄L3·（AgCF₃CO₂）₄]·0.75CH₃COCH₃（4）,which were obtained from the reaction of newly-synthesized tetraethynyl functionalized resorcin[4]arenes（H₄L1,H₄L2 and H₄L3）with silver（I）salts.In complex 1,four symmetry-related Ag₃ baskets are held together via Ag···Ag interactions to give a Ag₈unit,which are themunitedtogether by sharing four Ag（I）atoms to yield a remarkable Ag₁₂ cage.Finally,complex 1 was assembly comprising a Ag₁₂ cage sandwiched by two bowl-shaped resorcin[4]arene tetraethynides.2-4exhibit similar silver（I）chain structures.Moreover,the bowl-shaped resorcin[4]arenes are alternately decorated on two sides of the Ag（I）chain.In addition,the luminescence properties of 3 and the electrochemical properties of 3 and 4 have been investigated.2.Nine coordination polymers,[Tb（HL4）（C₂H₅OH）₂]（5）,[Eu（HL4）（C₂H₅OH）₂]（6）,[Gd（HL4）（C₂H₅OH）₂]（7）,[Sm（HL4）（C₂H₅OH）₂]（8）,[Yb（HL4）（C₂H₅OH）₂]·0.5H₂O（9）,[Cd₃（HL4）₂（DMF）₂（H₂O）₄]·4DMF（10）,[Zn₂L4（H₂O）]·DEF（11）,[Mn₂L4（DMF）（H₂O）₃]·2DMF·3H₂O（12）and[Co₂（HL4）（μ₃-OH）（H₂O）₂]·DMF·2.5H₂O（13）have been synthesized by resorcin[4]arene ligands with flexible tetracarboxylic groups.In compounds 1-6 and 9,H₄L is partiallydeprotonated to generate HL4^3-,while in 7 and 8,it is completely deprotonated.Compounds 5-9are isostructural and exhibitone-dimensional（1D）ribbon,and the ribbons arecombinedtogether by C-H···πinteractions to yield supramolecular layers,respectively.10forms a layer,and the layers are combined by hydrogen bonds to create a 3D supramolecular architecture.11 and 12 demonstrate 3D frameworks.Compound 13displays a double-stranded ribbon,where C-H···πinteractions and hydrogen bonds link adjacent ribbons to produce a supramolecular3D framework.The fluorescent behaviors of 5-11have been investigated.Compound5 is highly luminescent and shows sensing ability for acetone and Fe³⁺ions.3.Twonewresorcin[4]arene-basedcompounds,namely,[（CH₃）₂NH₂][Zn₃（HL5）（L5）（DMF）（H₂O）₂]·2H₂O（14）and[（CH₃）₂NH₂]₂[Cd₃（L5）₂（H₂O）₄]·2DMF·2H₂O（15）,have been synthesized undersolvothermal conditions（H₄L5）represents the resorcin[4]arene-based ligand).14 exhibits a layer structure,while 15 shows a 3D motif.Remarkably,by immersing 14 in an aqueous solution of Cu²⁺ions,a new compound[Cu₂（H₂L5）₂（H₂O）₂]·3.5H₂O（16）was achieved via a metal ion induced single-crystal-to-single-crystal（SCSC）transformation manner,involving generation of new metal-O bond and change of metal ion coordination geometry.Moreover,luminescent detection properties for Fe³⁺ions and Cr₂O₇^2-ions were also investigated with 14 and 15 as luminescent sensors.4.The properties of the synthesized trimeric molecule 1-NO₃ containing a cationic framework were studied.The anion exchange properties have been studied.In particular,1-NO₃ features efficient and selective removal of Cr₂O₇²ˉanions.When a mixture of 40-fold disturbing anions was employed,the Cr₂O₇²ˉsorption capability still remains a high efficiency.Moreover,the Knoevenagel condensation reaction was also explored by using 1-NO₃as an efficient heterogeneous catalyst.Noticeably,the catalytic activity of 1-NO₃ almost retains unchanged after four cycles.