Reaction Mechanism And Optoelectronic Properties Of Phthalocyaninato/Porphyrinato Complexes And Their Derivatives

Porphyrin and phthalocyanine and their derivatives are a series of macrocycle conjugated multi-pyrole compounds with broad application potential.The good coordination ability of porphyrin and phthalocyanine derivatives renders them coordinate with the most of metal ions easily.Moreover,the two-layer or multi-layer porphyrin/phthalocyanine compounds can be derived by coordinating with large metal ions and high coordination numbers.In addition,due to the ?-? interaction between macrocycle compounds,the easy modification in the chemical structures and the high chemical and thermal stability,porphyrin/phthalocyanine and their derivatives usually exhibit unique optical,electrical,magnetic and other properties,making them have potential application in organic photovoltaic cells,molecular catalysts,organic filed effect transitors(OFET)and photodynamic therapy medicals.Meanwhile,the aminopyridine compound with central N4 hole can also be used as ligand to construct metal-complex,revealing outstanding reactivity in CO2 electroreduction reaction.On the other hand,with the rapid advance of computer technology,the combination of theoretical calculations and experiments has gradually become a new trend in chemical researches.In this paper,the reaction mechanism of electroreduction of CO2 by tetrapyridine compound,the synthesis mechanism of dinuclear phthalocyanine and subphthalocyanine and the assembly of sandwich type(phthalocyaninato)(porphyrinato)compound and C60 together with their photoelectric and semiconductor properties were studied.The following aspects are the main research contents of this thesis:(1)The reaction mechanism of electrocatalytic reduction of CO2 by tetrapyridine cobalt compounds was studied based on density functional theory(DFT).In addition,the reaction of a series of novel aminotetrapyridine compounds has been well studied by changing the central metal,introducing a push-pull electron substituent at the pyridine para position,and replacing the bridge group.The results show that when the central metal is replaced by Cr,or an electron-donating substituent is introduced at the para position of pyridine,or a pair of bridge group is replaced with a p-? conjugated group,an electrocatalyst having better theoretical performance can be obtained.(2)The interaction between mixed(phthalocyaninato)(porphyrinato)yttrium triple-decker and fullerene in solution together with solid-state is clearly revealed by 1H NMR,electronic absorption,luminescence spectroscopies,single crystal X-ray diffraction analysis results and DFT calculations.The close interface between sandwich-type tetrapyrrole rare earth triple-decker and fullerene in cocrystals affords stronger charge transfer and thus a more effective photoelectric conversion responses than each individual.(3)OFET devices fabricated based on triple-decker mixed-(phthalocyaninato)(porphyrinato)yttrium(?)and fullerene cocrystals show high carrier mobilities of 3.72 and 2.22 cm2 V-1 s-1 for holes and electrons,respectively,at the interface of cocrystallized superamolecular layers,representing one of the most excellent cocrystal ambipolar OFET devices reported thus far.(4)Based on DFT calculation,the synthesis reaction mechanism of plane binuclear phthalocynine was studied.A stable intermediate was predicted by the present calculation results,which was then successfully isolated and characterized by1H NMR and mass spectrum results.In addition,the existence of ammonia predicted by calculation was also confirmed by experimental method.The present results provided mechanism support for the application of this cyclotetramerization reaction in further constructing covalent organic framework.(5)Based on DFT calculation,the formation mechanism of subphthalocyanine with phthalonitrile as the initial reagent mediated by boron trichloride in the solvent of xylene was systematically investigated.The elementary reactions with the formation of ?(C-N)bond are the rate-determining step in the whole reaction pathway.Moreover,despite as the reagent,the boron trichloride also facilitates the reaction by acting as a catalyst.However,the excessive boron trichloride would block and inactivate the active site.(6)Based on DFT,TD-DFT and CP-DFT,the second-order NLO property of a series of phthalocyanine-based molecules with different conjugated size and push-pull substituted groups were studied and the limitation was unveiled.An unusual octupole moment ESP population was found.