| The study on the novel coordination polymers is of current hot topic due to the structuraldiversity and the potential functional properties in adsorption, optics and magnetism. In situ ligandsynthesis has got considerable attention as an effective approach towards the crystal engineeringof coordination polymers. Some unusual organic ligands have been synthesized successfully,which are inaccessible or not easily obtainable via conventional methods. The hydrothermal in situacylation reactions between the organic polycarboxylic acids and N2H4H2O is one of the mostimportant kinds, which provide a new approach to obtain a series of coordinated polymerscontaining novel structure and excellent properties. However, less attention has been paid to thisreaction until now.Based on this mechanism, we synthesized thirty di（mono）acylhydrazidate-coordinatedcomplexes as well as two acylhydrazide molecules by the simple hydrothermal self-assembliesbetween metal salts, organic polycarboxylic acids and N2H4H2O sometimes in the presence ofH2ox, phen or bpy. We discussed the influence of pH and organic N-donor ligands etc. Not onlyresolved their single-crystal structure, also characterized them by element analysis, IR, XRD, TG,fluorescence spectra and magnetism. In order to understand the emission mechanism, the densityfunctional theory （DFT） calculations were carried out on the excited electronic states of somecompounds, which would supply theory basis between the relations of structures and functions forcoordination polymers. The paper includes seven chapters.In the first chapter, firstly, we concisely introduced the concepts, histories and sorts ofcoordination polymers. Secondly, we emphasized the mechanism and sorts of thehydro（solvo）thermal in situ ligand syntheses. Finally, we explained the research significance,innovation and the results in this paper.In the second chapter, we introduced the principle, methods and the reagent.In the third chapter, nine aromatic-monoacylhydrazidate-coordinated polymers as well as onemonoacylhydrazide molecule have been synthesized from the hydrothermal in situ acylationreactions:[Pb2（DCPTH）4（phen）2]（1）,[Cd3（DCPTH）2（dcph）2（bpy）2]（2）,[H（DCPTH）]（3）,[Pb2（MPTH）4（phen）2]（4）,[Cd2（MPTH）4（phen）2] H2O （5）,[Pb（APTH）2]0.25H2O （6）,[Cd2（APTH）4（phen）2]2H2O （7）,[Mn（APTH）2（H2O）]（8）,[Pb（CPTH）（phen）]（9）,[Pb4（OH）2（H2O）3（CPTH）3]·2H2O （10）（DCPTH=4,5-dichlorophthalhydrazidate, dcph=4,5-dichlorophthalate, MPTH=3-methylphthalhydrazidate, APTH=3-amiophthalhydrazidate,CPTH=4-carboxylphthalhydrazidate, phen=1,10-phenanthroline, bpy=2,2′-bipyridine）. In them, APTH derived from the hydrothermal in situ reduction reaction of NPTH（3-nitrophthalhydrazidate）, whereas the others derived respectively from the hydrothermal in situacylation reactions of corresponding organic polycarboxylic acids with hydrazine hydrate.Compounds1-3are containing DCPTH complexes. Compound1is a DCPTH-bridged chainedPb（Ⅱ） compound, with ancillary phen. It propagated into a3-D supramolecular network via π πinteractions and hydrogen-bonded interactions. Compound2is a DCPTH and dcph mixed bridgedchained Cd（Ⅱ） compound, with ancillary bpy. It is interesting that dcph also appeared in the finalframework of it. The π π interactions and hydrogen-bonded interactions make the crystalstructure more stabilizing. Compound3is only a monoacylhydrazide ligands. It propagated into a2-D supramolecular layer structure via intermolecular N-H O interactions between the acylaminogroups. Compounds4-5are containing MPTH inorganic coordination polymers. Compound4is aMPTH-bridged chained Pb（Ⅱ） compound, with ancillary phen. It propagated into a2-Dsupramolecular layer via π π interactions. Compound5is a MPTH-coordinated dinuclear Cd（Ⅱ）compound. It propagated into a1-D supramolecular chain via the O Ow interaction between theacylamino O atom and the lattice water molecule. Compounds6-8are containing APTH inorganiccoordination polymers. Compound6and8are APTH-bridged layered Pb（Ⅱ）/Mn（Ⅱ） coordinationpolymers. Compound7is an APTH-containing dinuclear Cd（Ⅱ） complex with ancillary phenmolecule. The2-D layer of compound6shows a wave-type, running down the c direction. It self-assembles into a3-D supramolecular network via the intermolecular N-H O interactions.Compound7self-assembles into a1-D supramolecular chain via hydrogen-bonded. Interestingly,in compound8, the amino N atom of APTH Ⅱ is also involved in the coordination to the Mn（Ⅱ）center. Compound9-10are CPTH-bridged layered Pb（Ⅱ） coordination polymers. Compound9self-assembles into a3-D supramolecular chain via π π interactions. Compound10areCPTH-bridged layered Pb（Ⅱ） coordination polymer with1-D Pb-O ribbons.There is a （H2O）8dimer. It self-assembles into a3-D supramolecular network via hydrogen-bonded.In the fourth chapter, twelve pyridine-monoacylhydrazidate-coordinated complexes havebeen synthesized from the hydrothermal in situ acylation reactions:[Zn（PDH）2（H2O）2]（11）,[Cd（PDH）2（H2O）2]（12）,[Pb（MPDH）2]（13）,[Cd（MPDH）2]（14）,[Mn（MPDH）2]（15）,[Co（MPDH）2（H2O）2]2H2O （16）,[Zn（MPDH）2（H2O）2]2H2O （17）,[Pb2（EPDH）4（H2O）]（18）,[Cd（EPDH）2（H2O）]（19）,[Mn（EPDH）2（H2O）2]（20）,[Co（EPDH）2（H2O）2]（21）,[Zn（EPDH）2（H2O）2]（22）,（PDH=pyridine-2,3-dicarboxylhydrazidate, MPDH=6-methylpyridine-2,3-dicarboxylhydrazidate, EPDH=5-ethylpyridine-2,3-dicarboxylhydrazidate）.Note that the acylhydrazidate all derived respectively from the hydrothermal in situ acylationreactions of corresponding organic polycarboxylic acids with hydrazine hydrate. Compounds14-15are1-D single-chained and18-19are1-D double-chained coordination polymers, the othersare the mononuclear molecular entities, but they all further self-assemble into the interestingsupramolecular networks via hydrogen-bonded interactions between pyridine-monoacyl hydrazidate ligands.In the fifth chapter, seven diacylhydrazidate-coordinated polymers as well as onediacylhydrazide molecule have been synthesized from the hydrothermal in situ acylation reactions:[Pb2（ODPTH）2（phen）2（H2O）2]（23）,[Cd（ODPTH）（phen）]0.25H2O （24）,[H2（ODPTH）]（25）,[Cd（BPTH）（phen）]3.75H2O （26）,[Pb2（DPHKH）2（phen）2]2H2O （27）,[Cd2（DPHKH）2（phen）]1.75H2O （28）,[Zn3（DPHKH）2（HDPHKH）2（phen）2]8H2O （29）,[Cd（SDPTH）（phen）（H2O）] H2O （30）（ODPTH=4,4′-oxydiphthalhydrazidate, BPTH=4,4′-biphthalhydrazidate, DPHKH=4,4′-diphthalhydrazidatoketone hydrazone, SDPTH=4,4′-sulfoyldiphthalhydrazidate）. Note that the diacylhydrazidate molecules in compounds23-30originated from the in situ acylation reactions between organic polycarboxylic acids andN2H4H2O. Interestingly, another kind of ligand in situ reaction was found in the formation processof DPHKH in compounds27-29: the nucleophilic addition reaction of the keto with N2H4H2O.Compounds23-25are containing ODPTH complexes. Compound23is an ODPTH-coordinateddinuclear Pb（Ⅱ） complex. It self-assembles into a2-D supramolecular layers via hydrogen-bonded.Compound24is an ODPTH-bridged chained Cd（Ⅱ） compound. Via the π π interactions betweenthe adjacent phen rings, the1-D chains further self-assemble into a2-D supramolecular sheet.Compound25is a new organic diacylhydrazide molecule. ODPTH shows a V-shape. Itself-assembles into a3-D supramolecular network through weak interactions. Compound26is aunique BPTH-bridged1-D double-chain Cd（Ⅱ） compound. Compounds27-29are containingDPHKH inorganic coordination polymers. Compound27is a DPHKH-coordinated Pb（Ⅱ）dinuclear compound. Pb（Ⅱ） is involved in a hemisphere-coordinated site. It is only extended into a1-D supramolecular chain owning to only one acylamino group head-to-head hydrogen bonds tothe adjacent acylamino group producing a hydrogen-bonded dimmer. Compound28and29areDPHKH-propagated chained Cd（Ⅱ）/Zn（Ⅱ） compounds with auxiliary phen molecule. Compound30is a SDPTH-extended chained Cd（Ⅱ） compound with auxiliary phen molecule.In the sixth chapter, two ox-extended Cd2+-monoacylhydrazidate coordinated polymers havebeen first synthesized from the hydrothermal in situ acylation reactions:[Cd2（ox）0.5（HPTH）（PTH）（bpy）2]（31）,[Cd2（ox）（PDH）2] H2O （32）（PTH=phthalhydrazidate, PDH=pyridine-2,3-dicarboxylhydrazidate, bpy=2,2′-bipyridine）. Note that the acylhydrazidate allderived respectively from the hydrothermal in situ acylation reactions of corresponding organicpolycarboxylic acids with hydrazine hydrate. Compound31is an ox-extended chained Cd2+-PTHcoordination polymer with ancillary bpy molecules. Neighboring bpy molecules between thechains form the π π packing, propagate the one-dimensional chains into a two-dimensionalsupramolecular layer. Compound32is an ox-propagated layered Cd2+-PDH coordination polymer.The layer exhibits a wave-like shape, extending along the b-axial direction. Noteworthily, oxexhibits a special μ6coordination mode.The solid-state fluorescence spectra show compounds1-3,5,7,9-14,17-19,22-25,30,32 possess good fluorescence emissions. They are the potential fluorescence materials. DFTcalculations have been applied to better understand the emission mechanism of compounds3,11,13,17,32. Two kinds of new charge-transfer paths are found in acylhydrazidate-coordinatedcompounds. Photoluminescence property in aqueous solutions have been studied on compounds4-5，23-25，27-30, all possess good fluorescence emissions, the charge transfer within the phenmolecule should be responsible for the emissions. Magnetic susceptibility datas for compounds8and20indicate antiferromagnetic interactions between Mn（Ⅱ） centers.In the seventh chapter, a brief conclusion and outlook are given. |
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