| Self-assembly supramolecular chemistry is a highly developed interdisciplinary subject,which covers the characteristics of chemistry,biology,physics etc.and has gradually developed into new research area.Herein,we reported and synthesized a series of functional molecules which was based on designing and synthesizing homofunctional organic ligands,using the concept of coordination-driven self-assembly and metal assembly-oriented programmed self-assembly.These functionalized metallic organic supramolecular molecules have potential applications in optical functional materials,catalysis et al.In the second chapter,a new series of anthracene derivatives1,1'-(anthracene-1,5-diyl)bis(ethan-1-one)and 1,1'-(anthracene-1,8-diyl)bis(ethan-1-one)were synthesized and both showed almost equal high yields in one pot.Based on the two anthracene derivatives,two new bis-?-diketone derivatives1,1'-(anthracene-1,8-diyl)bis(butane-1,3-dione)(H2L~1)and 1,1'-(anthracene-1,5-diyl)bis(4,4,4-trifluorobutane-1,3-dione)(H2L~2)have been designed and prepared for the synthesis of a series of cyclic dinuclear supramolecular complexes 1·2CH3OH and2·4CH3OH with Cu(II)and Eu(III)ions.In compound 1·2CH3OH,the ligands coordinated in a bidentate chelating manner,using the diketone function for coordination to the metal center and stabilizing of the chromophore by strong intramolecular hydrogen bonding between the unprotonated methanol and?-diketone groups with the pitch of 1.951(?)along the b axis.The triple stranded dinuclear structure of lanthanide bis-b-diketone complex 2·4CH3OH is obtained owing to the twistification of the two mono-?-diketone trifluoacetone groups of the ligand H2L~2.The preparation of the compounds reported in this paper offers a promising way to the design and synthesis of fascinating luminescent bis-?-diketonate architectures by varying the metal ions and ancillary ligand.In the third chapter,we designed and synthesized three types of bifunctional pyrazole ligands,these ligands have two different functional coordination sites.A series of first-level dimetal clips and secondary supramolecular compounds were synthesized through programmed self-assembly methods.The pyrazole functional groups of these bifunctional ligands can form a bidentate bridged coordination mode by spontaneous deprotonation in aqueous solution,leading to a series of first-level binuclear assemblies(terpy Pt)2(L~4)(NO3)3,(bpy Pd)2(L~5)2(NO3)2,(bpy Pd)2(L~6)2(NO3)2,(dmbpy Pd)2(L~5)2(NO3)2,(dmbpy Pd)2(L~6)2(NO3)2,(bpy2Pd2)2(L~7)2(NO3)2,(bpy2Pd2)2(L~8)2(NO3)2,a series of rare earth primary and secondary supramolecules Eu(L~4)3Na3,Tb(L~4)3Na3,Eu(terpy Pt)6(L~4)3(NO3)6,(HL7)3Eu(o Tf)3,and their structure was simultaneously synthesized and characterized NMR and mass spectrometry.Some of the assemblies were initially crystals.Because it is unstable in the air,its crystal growth conditions and related properties are under further study.At the same time,we studied the catalytic activity of C1-C4·2NO3-and C1-C4·2PF6-in the Suzuki coupling reaction.Combined with the bimetal directed assembly[(bpy)2Pd(NO3)2](NO3)2 or[(dmbpy)2Pd(NO3)2](NO3)2 with the raw ligands HL5 and HL6,we found that C1-C4·2NO3-and C1-C4·2PF6-had high catalytic activity in the Suzuki coupling reaction,which was attributed to nonnection between the Pd(II)and Pd(II)centers and the hydrogen bonding in the molecule.The study of these binuclear metal complexes is of great significance,and is still in progresswith further research.In the forth chapter,we designed and synthesized a series of bifunctional pyrazole ligands(HL~1,HL~2,HL~3,HL~4,HL~5,HL~6)and polypyridine ligands(L~7).The bifunctional pyrazole ligands have two different functions.A series of novel supramolecular compounds(C1·2NO3-,C2·2NO3-,C3·2NO3-,C4·2NO3-,C5·2NO3-,C6·8NO3-,C7·8NO3-,C8·36NO3-,C9·2NO3-,C10·12NO3-,C11,C12·2NO3-,C13·16NO3-,C14·2NO3-,C15·16NO3-,C16·2NO3-,C17·2NO3-,C18·2NO3-,C19·2NO3-,C20·24o Tf-,C21·24o Tf-)have been synthesized through programmed self-assembly method by combining the pyrazole functional group to spontaneously deprotonate in the solution system at room temperature.The functional pyrazole group of this two coordination site ligand forms a bidentate bridged coordination mode through spontaneous deprotonation in an aqueous system,and it interacts with the binuclear metal-oriented compounds([(bpy)2Pd(NO3)2](NO3)2 or[(dmbpy)2Pd2(NO3)2](NO3)2)"clips".A series of supramoleculars with bimetallic central cation skeletons were successfully obtained through self-assembly synthesis.The second coordination sites in these clip-type assemblies with[(bpy)2Pd(NO3)2](NO3)2 or[(dmbpy)2Pd2(NO3)2](NO3)2.The secondary coordination self-assembly synthesis was carried out to obtain a series of supramolecular structures with high charges and cationic framework.We use NMR and MS to track whether the assembly is complete,and characterize the target product through X-ray single crystal diffraction experiments,NMR,FT-IR,CSI-MS,and elemental analysis.In addition,we have studied the catalytic properties of the Suzuki-coupling reaction with C1-C4·2NO3-and C1-C4·2PF6-,all of the synthesized supramolecular compounds have good catalytic activity in the Suzuki-coupling reaction duing to the existence of Pd(II)···Pd(II)bonds cooperation and intermolecular hydrogen bonding in the molecules.In the fifth chapter,we have designed and synthesized six carbon disulfide ligands.Through AuI···AuI bonding interactions,we reported the synthesis of a series of homochiral tetramers bulk metal Au16 ring with AuI···AuI bonding interactions.We synthesized four boat-shaped monomers{[(dppm)Au2]2L2-}·2PF6 as the primary building units,and synthesized secondary chiral cyclic supramolecular compounds through intermolecular induction.Among them,the four corresponding homochiral{[(dppm)Au2]2L2-}·2PF6 self-assembly through strong intermolecular metal-metal bonds and interactions.At the same time,the single crystal X-ray diffraction structure analysis of the complex 14-64·8PF6 showed that it is a homochiral tetrameric metal macrocyclic structure.In addition,NMR characterizations and analysis have been tested under the influence of concentration and temperature,the complex 14-64·8PF6undergoes programmable self-assembly to synthesize the homochiral tetrameric metal Au16 through directional AuI···AuI bonding interactions.Interestingly,it has been successfully determined that 14,64 and 84·8PF6 are almost all optically pure homochiral crystals.And based on the single crystal structure characterization datas,we proposed a reasonable way to induce accumulation between dimers,which was further proved by the crystal data of 54 and 64·8PF6.This phenomenon of homochiral self-assembly provides us a visual window to better understanding the programmable self-assembly synthesis driven by the directional AuI···AuI bonding interaction in our experimental synthesis.The mechanism of assembly and disassembly of homochiral tetrameric metal Au16 macrocycles is discussed.At the same time,these chiral aggregates with metal-metal bond interactions also show potential applications in chiral molecular recognition and chiral storage materials. |
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