Synthesises And Properties Of Schiff-base Macrocyclic Compounds And Relative Supramolecular Systems Based On Novel Extended Dialdehydes

As a multidisciplinary domain,supramolecular chemistry is very popular at the frontier of research for a long time.Usually,supramolecular chemistry focuses on the ordered aggregations involved non-covalent interaction(supramolecular forces).Its basic researches contain the organic chemistry and synthesis of targeted molecules,coordination chemistry and complexes,physical chemistry and the theoretical study of interaction force,biochemistry and biological processes,materials science and the relative properties,etc.The supramolecular chemistry is in the intersection of chemistry,physics,biology and material science.At the same time,it also learns the merits of these disciplines to overcome the challenges of energy,material,information technology and life science.Here this dissertation,i.e.,'Synthesises and Properties of Schiff-base Macrocyclic Compounds and Relative Supramolecular Systems Based on Novel Extended Dialdehydes',is carried out in this background.After the aborative study of literatures,we start a new research from the idea of flexible extended dialdehydes with larger sizes which is inspired by the previous results of functional macrocyclic complexes based on 2,6-diformyl-4-chlorophenol.Meanwhile,we successfully obtain series of pendant-armed Schiff-base macrocyclic complexes after the cyclic condensation reaction between these dialdehydes and compatible diamines in the presence of metal ion templates.In order to keep up with latest tendency,we also explore the relative properties of these new Schiff-base macrocyclic compounds in the field of supramolecular chemistry and material science.In total,on the one hand,this paper expands the contents of Schiff-base macrocyclic compound.On the other hand,it also enriches the theory of supramolecular chemistry and macrocyclic chemistry.Especially,it might apply new thoughts to solve key technical problems of molecular informatics in the field of information science.Specifically,the main work of this paper is divided into the following seven parts:Chapter 1:Introduction.Here we focus on the critical concepts and theories,difficulties and applications in the field of Schiff-base macrocyclic compounds and pave the way for latter research thoughts and results.Firstly,we describle the development of supramolecular chemistry and macrocyclic chemistry which are the two main themes.It contains the type of the Schiff-base macrocyclic compound,related theories and concepts and frontier applications.At the same time,we discussed the unique schiff base macrocyclic compounds containing dynamic covalent bond in detail.These include a review of chemical properties of schiff base imine bond,the history of schiff base macrocyclic compounds,dialdehyde and diamine precursor compounds,the synthesis of Schiff-base macrocyclic compounds and relative researches of application.At last,we introduce the significances and approaches of this topic upon the previous works.Chapter 2:Construction of pendant-armed Schiff-Base macrocyclic dinuclear zinc complexes and their selective recognition of acetate ion.Syntheses,spectrum,single-crystal structure and selective recognition of anion for two Schiff-base macrocyclic dinuclear Zn(?)complexes are described here.Two new flexible extended dialdehydes(H2hpdd and H2pdd)with different functional pendant arms(-CH2CH2PhOH and-CH2CH2Ph)have been designed and synthesized,and they are used to react with 1,2-bis(2-aminoethoxy)ethane to prepare Schiff-base macrocyclic complexes in the presence of Zn(?)ion template.As a result,two pre-organized dinuclear Zn(?)intermediates(1 and 2)as well as two 46-membered folded[2+2]macrocyclic dinuclear Zn(?)complexes(3 and 4)are produced,respectively.It is noted that the central zinc ions show distinguishable coordination fashions with dialdehydes and[2+2]macrocyclic ligands in 1-4,where the subtle pH adjustment function of two pendant arms(with or without the phenolic hydroxyl group)is believed to play vital roles.Furthermore,cation and anion recognization experiments for complexes 3 and 4 reveal that they can selectively recognize acetate ion by forming 1:1 stoichiometric complexes,which can be verified by the alterations of UV-vis and ESI-MS spectra and even naked eyes.These results reveal that the Schiff-base macrocyclic metal complexes may be outstanding substrates for the recognition of some receptors in the supramolecular chemistry.Chapter 3:Distinguishable Zn(?)and Pb(?)template effects on forming pendant-armed Schiff-base macrocyclic complexes including a unprecedented Pb(?)-? macrocyclic complex.Syntheses,spectrum,single-crystal structure for two Schiff-base macrocyclic dinuclear Zn(?)complexes and two Schiff-base macrocyclic mononuclear Pb(II)complexes are described here.And we also carefully study the specific supramolecular Pb(?)-? interaction in a relative Pb(?)-?complex.36-Membered[2+2]half-fold Schiff-base macrocyclic dinuclear Zn(II)complexes(la and 1b)and 18-membered[1+1]Schiff-base macrocyclic mononuclear Pb(?)complexes(2 and 3)are produced from the condensation between 1,3-propanediamine and a pair of extended dialdehydes with different functional pendant arms(H2hpdd and H2pdd)because of the distinguishing cationic template effects.It is very interesting to mention that a unique intramolecular Pb(?)-?macrocyclic complex 2 with an uncommon ?3-coordinated type is achieved under ambient condition and it can keep stable both in the solid state and in solution.The subtle variations of pendant-arms in the macrocyclic ligands H2hpdd and H2pdd yield different Pb(?)complexes,where the competition between Pb(?)-? and Pb(II)-NO3-electrostatic interactions as well as the combination of steric and electronic effects of pendant arms is believed to play important roles.Chapter 4:Influence of pendant arm,halide and solvent on high-efficient tuning[1+1]and[2+2]Schiff-Base metallomacrocycles via zinc ion template.Syntheses,spectrum,single-crystal structure for seven relative pendant-armed[1+1]and[2+2]Schiff-base macrocyclic Zn(II)complexes 1-7 which could be selectively regulated by pendant arm,halide and solvent are described here.A series of pendant-armed Schiff-base macrocyclic complexes 1-7 has been prepared by the condensation between extended dialdehydes with pendant arms(H2hpdd/H2pdd)and 1,3-propanediamine in the presence of ZnX2(X = Cl,Br,I),where 18-membered[1+1]mononuclear and 36-membered[2+2]half-fold trinuclear macrocyclic Zn(?)complexes are yielded.Three experimental variables,i.e.,pendant arm,halide and solvent,are found to influence the organization of final macrocyclic complexes,in addition to the conventional metal ion template effect promoting reversible formation and cleavage of Schiff-base imine bonds.It is noted that all the reactions produce singular macrocyclic complexes in high yields if the experimental variables are fixed,and the selection of different pendant arms and halide counterions will generate different[1+1]mononuclear and[2+2]trinuclear macrocyclic Zn(?)complexes.More interestingly,[1+1]and[2+2]macrocyclic Zn(?)complexes 2 and 3 can be produced in methanol and ethanol,respectively,in the case of the reaction between ZnBr2,H2pdd and 1,3-propanediamine.Further experiments reveal that red solid 2 and yellow green solid 3 can be transformed to each other just by altering the type of solvents,and this tuning is complete and reversible.Chapter 5:Anion-induced restructuring of Schiff-base macrocyclic zinc complexes:ring contraction and self-assembly into a molecular box.Syntheses,spectrum,single-crystal structure for four Schiff-base macrocyclic Zn(?)complex derivring from the restructurings of two Schiff-base macrocyclic Zn(?)complexes are described here.And we also carefully study the mechanism of these two supramolecular processes.Two reported 46-membered[2+2]flexible Schiff-base macrocyclic dinuclear Zn(?)complexes(la and 1b)containing different pendant arms are used here.Induced by the specific anion(SCN" and N(CN)2-),two macrocyclic complexes(la and 1b)can achieve ring contraction or supramolecular self-assembly.Under the linear SCN' anion,two macrocyclic complexes both could carry out ring contraction.And the macrocyclic complex la simultaneously degrades into the 23-membered[1+1]Schiff-base macrocyclic mononuclear Zn(II)complex 2 and dinuclear Zn(II)complex 3 while lb only transforms into the macrocyclic complex 5 like analogous 2.In the case of pseudolinear N(CN)2-anion,self-assembly happens here.But only the macrocyclic complex la can self-assemble into a molecular box 4 and the similar self-assembly and analogous molecular box could not be achieved for lb.Finally,we confirm that these entirely different results under the same anions are ascribed to the subtle regulation of pH value by the different pendant arms on the skeletons of complexes la and lb.Chapter 6:The[2+2]Schiff-base macrocyclic ligands assemblied by both Ln(?)and Zn(?)template ions:efficient NIR Yb(?)sensitizers.Syntheses,spectrum,single-crystal structure for two Schiff-base macrocyclic dinuclear Zn(?)complexes and five Schiff-base macrocyclic mononuclear Ln(?)complexes are described here.Identical two 34-membered[2+2]pendant-armed Schiff-base macrocyclic ligands(H4La and H4Lb)can be constructed via the reactions between rigid o-phenylenediamine and extended dialdehydes(H2hpdd/H2pdd)in the presence of either Ln(?)or Zn(?)template.The triplet(3??*)excited state energy levels of two macrocyclic ligands(H4La and H4Lb)which are determined from corresponding Gd(?)complexes in solid at 77 K are both 19120 cm-1 indicating appropriate candidates for efficient Yb(?)NIR sensitizers.Finally,it is very interesting to mention that corresponding two mononuclear Yb(?)macrocyclic complexes(1 and 7)exhibit characteristic near-infrared emission at 974 nm with high quantum yields about 1%in solution.X-ray diffusion analysis reveals that the sandwich-like complex configurations,which contain eight-coordinated Yb(?)centres surrounded by Schiff-base macrocyclic ligands,prevent the fluorescence quench from the competitive coordination of solvents,counterions and other molecules and enhance the intramolecular ligand-to-ytterbium energy transfer.Chapter 7:Base-induced self-assembly for one-dimensional coordination polymers via chiral pendant-armed Schiff-base mononuclear Pb(II)macrocycles.Syntheses,spectrum and single-crystal structure for four Schiff-base macrocyclic mononuclear Pb(II)complexes are described here.Two new chiral flexible extended dialdehydes(R-H2pabb and S-H2pabb)with different chiral functional pendant arms have been designed and synthesized,and they are used to react with 1,3-propanediamine to prepare Schiff-base macrocyclic complexes in the presence of Pb(II)ion template.In result,a pair of 18-membered[1+1]chiral pendant-armed Schiff-base macrocyclic mononuclear Pb(II)complexes(R-1 and S-1)with an unusual N1O2 coordination mode are synthesized from two chiral isomeric dialdehyde precursors.Moreover,they both can be further self-assembled to relative one-dimensional chiral ribbon coordination polymers(R-2 and S-2)by adding NaOH as a base to remove two phenolic protons.