Design, Synthesis And Properties Of Novel Oligomers With Porphyrinato And Phthalocyaninato Ligands

Porphyrin, phthalocyanine and their derivatives are important kinds of dyes and pigments with the significant potential application, which share the same cyclic tetrapyrrole molecular. As the typical representatives of functional molecular with macrocyclic structures, porphyrin and phthalocyanine derivatives have good coordination ability, and most of the periodic table metal ion reactions can be their metal complexes (e.g. lanthanides, actinides, and some main group elements). In particular, with large metal ions and high coordination numbers, the complexes are either monomeric species with the metal ion out of the N4plane or double-and triple-decker counterparts with the metal sandwiched between two neighboring tetrapyrrole ligands, the latter compounds can be called sandwich-type complexes. The typical molecular characters, including the strong intramolecular π-π interaction, multi-reversible and stable oxidation states, and chemical modification in the molecular structure. In addition, porphyrin, phthalocyanine and its complexes usually has high chemical stability, thermal stability. The unique optical, electrical, magnetic and other properties making it the new type of molecular machines, spectroscopy and electrochemistry, molecular recognition, field effect transistor, and liquid crystals, etc have broad application prospects. In this thesis, a series of novel homo-and heterdimetallic homobinuclear phthalocyaninato complexes with same substituent group, trisporphyrin and planar binuclear phthalocyanine-containing sandwich-type rare-earth complexes are designed and synthetized with their structure and properties well researched. The following three topics are the main research contents:1Novel Homo-and Heterodimetallic Homobinuclear Phthalocyaninato Complexes. Synthesis, Structure, Spectroscopy, and ElectrochemistryDue to extended π electronic structure, conjugated planar binuclear phthalocyanines with valence metal have been the focus of significant research interest since their special optical and electrochemical properties. These compounds with synthesis, characterization and electrochemistry are rarely reported. In addition, the structure of planar binuclear phthalocyaine have not been obtained on the basis of single crystal X-ray diffraction analysis with the low solubility cause of the strong intramolecular π-π interaction. In this chapter, we designed and synthesized a series of novel homo-heterodimetallic homobinuclear phthalocyaninato complexes MPc(OR)6-M’Pc(OR)6[M=M’=Co, Ni, Mn; M≠M’, M=Co, M’=H2, Ni, Mn]. These binuclear phthalocyanine compounds were characterized by a series of spectroscopic methods including mass, electronic absorption,’H NMR, IR spectroscopy and elemental analysis in addition to X-ray single crystal diffraction analysis. Moreover, their electrochemical data over these binuclear phthalocyanine compounds have also been provided by cyclic voltammetry and differential pulse voltammetry measurements. In particular, their binuclear phthalocyanine nature has been directly revealed on the basis of single crystal X-ray diffraction analysis of the homo-dicobalt species CoPc(OR)6-CoPc(OR)6for the first time. This result will be helpful towards understanding the structure property relationship of binuclear phthalocyanine compounds with planar conjugated electronic structure. In addition, the only one redox couple of CoⅡ/CoⅠand MnⅡ/MnⅠ were confirmed by the systematic studying of electrochemical data of all these compounds. It futher proved the feasibility about the synthesis route of heterodimetallic homobinuclear phthalocyaninato complexes.2Trisporphyrin with1,3,5-Triazine Core:Synthesis, Spectroscopy, and Self-Assembly PropertiesIn this part, under strong acid conditions with trifluoromethanesulfonic acid, H2TPCNPP underwent a trimerization reaction in chloroform to afford trisporphyrin. Reaction of this metal free ligand with zinc acetate led to a Zn trisporphyrin. These compounds were characterized by a series of spectroscopic methods including mass,1H NMR,1H-1H COSY, electronic absorption, and IR spectroscopy in addition to elemental analysis. The self-assembly process has been systematic studied by the titration experiments based on the UV-vis and1H NMR spectroscopy. There are two isoabsorptive points for this Zn trisporphyrin with adding DABCO at1×10-5M, while only one isoabsorptive point at1X10-6M. A intermediate2:3sandwich complex was obtained at1X10-5M of trisporphyrin. This intermediate was also observes in the1H NMR spectra at low temperature. With adding DABCO, the proportion of2:3sandwich complex is increasing until vanish of other species. In addition, The calculated value for binding constants K1is (6.4±0.2) X1022M-4based on the simultaneous fitting of the titration data for the formation of the assembly and for its destruction. The values of EM was calculated form the equation K1=Km6EM1EM2. Thus, the geometric average of the EM values is0.002M. These results indicat the relationship between the concentration of different species and the host concentration.3Planar Binuclear Phthalocyanine-Containing Sandwich-Type Rare-Earth Complexes:Synthesis, Spectroscopy, Electrochemistry, and NLO PropertiesThe mixed cyclic tetramerization of4,5-bis(hexylthio)-phthalonitrile and bis(diiminoisoindoline) with [M(acac)3]-nH2O (M=Pr, Eu, Lu) as template in the presence of1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol at reflux has provided binuclear phthalocyanine-containing sandwich-type rare-earth complexes [{Pc(SC6H13)8}M{BiPc-(SC6H13),2}M(SC6H13)8](M=Pr, Eu, Lu). These new binuclear phthalocyanine-containing sandwich compounds have been characterized by a series of spectroscopic methods including mass spectrometry and’H NMR, electronic absorption, and IR spectroscopy in addition to elemental analysis. Their electrochemical data have also been obtained by cyclicvoltammetry. In addition, the third-order nonlinear optical properties of [{Pc(SC6H13)8}Pr{BiPc(SC6H13)12}Pr(SC6H13)8] and [Pr{Pc(SC6H13)8}2] in toluene solution were studied comparatively by using the Z-scan technique; effective imaginary third-order molecular hyperpolarizabilities of1.86-10-11and1.56-10-11esu, respectively, were obtained, which indicates their potential application in the optical-limiting field.