| The design and construction of new functional coordination polymers have been one of the frontier and final goals in current crystal enginerring due to their intriguing topological structures and potential applications in the fields of optical, catalytic, molecular recognition, gas storage and biology activity. Although many coordination polymers with unusual structures have been constructed depending on the self-assembly, the exploration for preparing functional coordination polymers still remains a challenge. Therefore, in further designing coordination polymers possessing interesting structural motifs and properties, the elaboration of organic ligands, the choice of metal ions and the controlling of reaction conditions are of significant importance. In the thesis, 21 d10 transition /lanthanide coordination polymers based on four series of organic ligands were designed and constructed by hydrothermal methods, [Zn2(pam)2(2,2'-bpy)2] (1), [Cd(pam)(2,2'-bpy)2]n (2), [Zn(pam)(phen)]n (3), [Cd(pam)(phen)]n·0.5nCH3CH2OH·0.5nH2O (4), [Zn(pam)(4,4'-bpy)]n·0.5n CH3CH2OH (5), {[Cd5(μ3-OAc)2(μ2-OAc)2(μ3-OH)2(pam)2(4,4'-bpy)2]·CH3CH2OH}n (6), [Cd(btc)0.5(2,2'-bpy)]n (7), [Cd(btc)0.5(phen)]n·nH2O (8), [Zn(btc)0.5(H2O)]n (9), {[Zn(btc)0.5(4,4'-bpy)0.5(H2O)]·1.5H2O}n (10), {[Zn2(H2btc)2(4,4'-bpy)4]·H2O}n (11), [Zn(H2btc)(bpe)]n (12), [Ln2(Hpdc)2(C2O4)(H2O)4]n·2nH2O [Ln=Sm (13), Eu (14), Tb (15), Dy (16)], [Cd(batpy)2]n·nH2O (17), [Ln(batpy)3]n [Ln=Sm (18), Tb (19), Eu (20), Dy (21)] (H2pam=pamoic acid, H4btc=biphenyl-3,3',4, 4'-tetracarboxylic acid, H3pdc=3,5-pyrazoledicarboxylicacid, Hbatpy=4'-(C6H4-p-COOH)-2,2':6',2"-terpyridine). The totals of 21 coordination polymers were characterized by elemental analyses, IR spectra, X-ray single crystal diffraction, thermal gravimetric analyses, and luminescence analyses. The results are following: (1) The controllable mechanisms of the influence of auxiliary ligands containing N and metal ions on the framework and properties of their coordination polymers are divided into two types: (i) In a comparison of the structures of coordination polymers 1, 3, 5, it was found that the final structure can be tuned by the steric hindrance of ligands containing N; (ii) In a comparison of the structures of coordination polymers 2, 4, 6, it was found that the final structure can be tuned by the influence of ligands containing N on carboxyl coordination modes. In addition, by inspection of the structures of coordination polymers 1, 3, 5 and 2, 4, 6, it was found that the final structure can be tuned by the size of metal ions according to the controllable mechanisms of (ii).(2) By rational adjustments of auxiliary ligands containing N and pH value at present system, polymers 7, 8, 9, 10, 11, 12 were successfully synthesized by hydrothermal methods. Among these polymers: polymer 9 possesses a helical bilayer structure pillared by btc anion; polymer 10 is a double-layered supramolecular motif generated by H-bonds interactions; polymer 11 displays a supramolecular bilayer network formed by double chains; polymer 12 features a double-layered framework linked byμ2-carboxyl groups.(3) The synergetic operation of Sm3+ and Cu2+ metal ions can lead to in situhydrothermal generation of C2O42- from(Hpdc)2-. Inspired by the reaction, four 3Dlanthanide polymers (13, 14, 15, 16) possessing regular frameworks and luminescent properties were successfully synthesized by hydrothermal methods. The results show that transition intensity changes in the order of Tb3+ > Eu3+ > Dy3+ > Sm3+.(4) Four 1D lanthanides polymers (18, 19, 20, 21) with one batpy ligand and one 1D d10 metal polymer (17) were successfully synthesized by hydrothermal methods, Furthermore, polymers 17 and 20 are two potential blue and red fluorescence materials due to its very high thermal stability and luminescent intensity.
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