Design,Synthesis,and Properties Of Conjugated Cyclic Oligopyrroles With Extended ? Electronic Structure

Phthalocyanines are conjugated macrocyclic tetrapyrrole compounds of 18?-electron aromaticity,which are analogous to naturally occurring porphyrins.In recent years,the phthalocyanine based materials have aroused great interest of scientists,due to their special skeleton structure,which could be screened and assembled by introducing central ions,axial ligands and substituted groups,and thus obtained materials with special physical and chemical stabilities,as well as photochemical,electrochemical,photocatalytic and other functions.It is also well known that porphyrinato phthalocyaninato ligands can form sandwich-type complexes with various rare earth metal ions.These sandwich-type double-decker compounds show many excellent optical,electronic,and magnetic properties due to the large ?-conjugated system,strong ?-? interactions between two macrocycles,heavy lanthanide ions,and one-electron radical character,endowing them a great application potentials as nonlinear optical materials,gas sensors,organic field effect transistors,and single molecular magnets.Subphthalocyanines are lower homologues of phthalocyanines,containing three pyrrole units with 14 ?-electron aromatic system and cone-shaped molecular conformation have also received intense attention as new function pigments in recent years.Fusion of additional aromatic moieties onto the phthalocyanine or subphthalocyanine periphery has been found very much effective in substantially tuning their optical and electrochemical properties for the purpose of enhancing their application-related functionalities.This is also true for double-deckers.In this thesis a series of novel phthalocyanine and subphthalocyanine derivatives and heteroleptic bis(phthalocyaninato)europium double-decker complexes have been designed and synthetized,with their structures and properties well researched.The following three topics are the main research contents:(1)Novel pyrene-fused unsymmetrical phthalocyanine derivatives Zn[Pc(Pz-pyrene)(OC8H9)6](1)and Zn[Pc(Pz-pyrene)2(OC8H9)4](2)were isolated for the first time.These unsymmetrical pyrene-fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods.In particular,the pyrene-fused phthalocyanine nature was unambiguously revealed on the basis of single crystal X-ray diffraction analysis of Zn[Pc(Pz-pyrene)(OC8H9)6](1),representing the first structurally characterized phthalocyanine derivative fused with aromatic moiety larger than benzene.(2)A series of four phenanthro[4,5-fgh]quinoxaline-fused SubPc derivatives 0-3 containing zero,one,two,and three phenanthro[4,5-fgh]quinoxaline moieties,respectively,were characterized by a series of spectroscopic methods including MALDI-TOF mass,'H NMR,electronic absorption,magnetic circular dichroism(MCD),and fluorescence spectroscopy.The molecular structures for the compounds 0 and 2 were clearly revealed on the basis of single crystal X-ray diffraction analysis.Along with the increase in the number of the fused-phenanthro[4,5-fgh]quinoxaline moieties,both the first oxidation and first reduction potentials gradually shift in the positi-ve direction,due mainly to the electron-withdrawing nature of the phenanthro[4,5-fgh]quinoxaline moiety were also studied by cyclic voltammetry.Furthermore,theoretical calculation in combination with the electronic absorption and electrochemical analysis reveals the significant influence of the fused-phenanthro[4,5-fgh]quinoxaline units to the electronic structures.(3)Mixed cyclic tetramerization of 5,6-dicyano-2-(4,5-bis(amylthio)-1,3-dithio-2-ylidene)-benzo[d]1,3-dithiole and 1,2-dicyanobenzene with half-sandwich complex Eu(Pc)(acac)as template in the presence of DBU in refluxing n-pentanol led to the formation and isolation of a series of unprecedented tetrathiafulvalene(TTF)-fused heteroleptic bis(phthalocyaninato)europium double-deckers Eu(Pc)[Pc(TTF)n](n=1-4)(1,2-cis,2-trans,3,and 4).Electronic absorption spectroscopic results reveal the effect of fusing TTF onto the phthalocyanine chromophore of double-decker on the electronic structure of the target compounds.ESR together with the IR and electronic absorption spectra disclose the existence of unpaired electron in the newly prepared heteroleptic complexes.In particular,in addition to the Pc-chromophore based one-electron redox processes,one-electron,two-electron,three-electron,and four electron oxidation processes were clearly revealed by the electrochemical technique for the one-TTF,two-TTF,three-TTF,and four-TTF moiety-fused double-decker 1,2-cis and 2-trans,3,and 4,respectively,indicating the significant influence of the TTF moieties fused to the double-decker electronic structure.In particular,theoretical calculations over 0 and 4 in combination with the electronic absorption spectroscopy reveal the significant influence of the fused-TTF units to the electronic structure.(4)a novel cruciform conjugated pentanuclear phthalocyanine was designed,synthesized,and characterized for the first time.The water-soluble nanoparticles assembled from this single molecular material with the help of DSPE-PEG2000-OCH3(Zn4-H2PC/DP NPs)exhibits characteristic absorption in NIR ? region at 1064 nm with a large extinction coefficient of 52 L g-1 cm-1,high photothermal conversion efficiency of 58.3%,and intense photoacoustic signal.Moreover,both in vitro and in vivo studies reveal the good biocompatibility and notable tumor ablation ability of Zn4-H2PC/DP NPs in the second NIR window.