| In the past few decades,the exploration of coordination polymers and metal-organic frameworks based on self-assembly synthesis from a large number of metal ions with organic linkers have attracted explosive attention as an emerging type of functional materials because of their outstanding functional properties and a variety of remarkable and practical applications.It is certainly true that the diversity and complexity of the structures determines the diversity of its properties.However,the design and option of organic ligands is an important method controlling the structure of coordination complexes,the semi-rigid carboxylic acid ligands with the V-type structure can be adjusted according to the coordination mode of metal ions in the self-assembly process to synthesize the desired functional polymers.Hence,we have selected two novel ether-oxygen bridged semirigid tricarboxylate ligands,5-?4-carboxyphenoxy?nicotic acid?H2cpna?and 2-?2-carboxyphenoxy?terephthalic acid?H3cpta?as main building blocks and tested them in the hydrothermal self-assembly reactions with different metal salts.Then,we gained twenty-six coordination polymers which have different configurations,high thermal stability,good fluorescence and magnetic properties.All of the promising coordination compounds are tested by single-crystal X-ray diffraction and we obtained their topology structures by using Topos.They also are characterized by infrared spectroscopy,powder X-ray diffraction,elemental,and thermal analyses.Furthermore,the optical and magnetic properties of the complexes have also been discussed.This article contains three chapters and the main profile is as follows:Chapter 1:This chapter briefly introduced the perspectives and importance of coordination chemistry,and the synthesis methods and architecure of coordination polymers.Moreover,the diversity of crystal structure,main influencing factors,and the potential application value or application in the reality of the coordination polymers were mentioned.Chapter 2:We constructed thirteen novel coordination compounds?1–13?derived from H2cpna by hydrothermal synthesis.H2cpna as a main building block,in the prescence of metal nitres?Ni?,Cd?,Mn?,Zn?,Co?,Cu?,and Pb??,available ancillary ligand 2,2?-bipyridine?2,2?-bipy?,bis?4-pyridyl?amine?bpa?,1,10-phenanthroline?phen?,or 4,4?-bipyridine?4,4?-bipy?.Weformulatedtheproductsas[Co??3-Hcpna?2]n?1?,[Mn??4-cpna??H2O?]n?2?,[Mn??4-cpna??H2O?2]n?3?,[Mn??-cpna??2,2?-bipy??H2O?2]n?4?,{[Ni??3-cpna??2,2?-bipy??H2O?]2·H2O}n?5?,{[Cd??3-cpna??2,2?-bipy?]·2H2O}n?6?,[Zn2??-cpna?2?2,2?-bipy?2][Cu??-cpna??2,2?-bipy??H2O?]n?7?,?8?,{[Mn??-cpna??phen?2]·6H2O}n?9?,{[Ni??3-cpna??phen??H2O?]·H2O}n?10?,[Zn2??-cpna?2?phen?2]?11?,{[Pb??3-cpna??phen?]·H2O}n?12?,[Ni??3-cpna??4,4?-bipy?0.5?H2O?]n?13?.We discussed coordination moods and structure characteristics derived from H2cpna.The structures of 1–13 vary from a discrete 0D cyclic dimer to the 3D metal-organic frameworks.The results of analysis indicated that various factors affect the structure of the coordiation polymers,such as the type of metal ion,the pH of the solution,the auxiliary ligand and the template.Topological analys is showed that complex 2 had a rare hxg-d-4-C2/m topology.Besides,the optical and magnetic properties of the coordiation polymers have also been discussed.Chapter 3:We constructed thirteen newfangled coordination compounds?14–26?derived from H3cpta by hydrothermal synthesis.H3cpta as a main building block,in the prescence of metal nitres?Mn?,Cd?,Ni?,and Zn??,alternative ancillary ligand 2,2'-biimidazole?H2biim?,pyridine?py?,1,10-phenanthroline,or 2,2-bipyridine.The products were named as[Cd??-Hcpta??phen??H2O?]n[Mn??-Hcpta??phen??H2O?]n?14?,?15?,{[Cd3??6-cpta?2?py?2]·5H2O}n{[Cd3??3-HL???4-L???-Cl??H2O?4]·2H2O}n?16?,?17?,[Mn3??5-cpta?2?2,2?-bipy?2]n?18?,?19?,[Mn3??4-cpta?2?phen?3?H2O?2]n{[Cd2??4-cpta???-Cl??phen?2]n{[Zn3??3-cpta?2?phen?3]·3H2O}n{[Cd3??5-cpta?2?phen?2?H2O?2]n?20?,?21?,?22?,?23?,[Cd3??4-cpta?2?phen?3?H2O?2]n[Cd3??5-cpta?2?H2biim?2]n?24?,[Zn2??6-cpta???-Hbiim?]n?25?,[Ni3??3-cpta?2?phen?3?py?3?H2O?3]n?26?.The coordination modes and structure characteristics of H3cpta were discussed.The structures of 14–26 vary from a discrete 0D dimer to the 3D metal-organic frameworks.Such a wide structural diversity of 14–26 is guided by the following factors:a type of metal?II?ions and counter anion,a deprotonation degree of the principal H3cpta block,and type of an auxiliary ligand.Topological classification showed some topologically unique nets?in 16,17,and 25?.Besides,the optical and magnetic properties of the coordination polymers have also been discussed,17 can be used as a sensitive material for the detection of Fe3+ions in aqueous solution through the luminescence quenching effect. |
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