A Theoretical Study On The Nature Of The Interaction Between Phthalocyanine And Fullerene Molecules

Free-base phthalocyanine/metal phthalocyanine and fullerene have excellent physical and chemical properties respectively.The supramolecular compounds assembled by them have broad application prospects in organic solar cells,nonlinear optics and optoelectronic functional materials.The systematic and regular research results on the nature of intermolecular interactions play high instruction values for experimental work and material application and development.However,there is no scholar to study the interaction between molecules in theoretical calculations.The density functional theory they used was not accurate enough.Moreover,they only calculate a portion of metal phthalocyanines.Thus,the nature of the interaction cannot be explained systematically.In particular,some research work uses small base sets and does not correct the basis set superposition error.On the other hand,the correction value of basis set superposition error is negative,which completely violates the definition of basis set superposition error.It exposes the obvious errors in the energy calculation results completely.Therefore,the results of previous studies on the interaction of free-base phthalocyanine/metal phthalocyanine and fullerene cannot provide high instruction values.This paper uses reliable quantum chemistry methods to study the nature of interaction comprehensively and systematically.In the calculation of monomolecular system,B3LYP is a very successful and classic density functional method.Therefore,we use this method to optimize the electronic state of the metal phthalocyanine.The TPSS-D3(BJ)method was carefully selected by Professor Grimme,which is widely used in the supramolecular geometry optimization.Therefore,we use the reliable TPSS-D3(BJ)method to optimize the geometry of the complex in this article.In recent years,Professor Head-Gordon adopted the?B97M-V method for the main group elements.We choose this method which is not only used to calculate the interaction energy between transition metal phthalocyanine and fullerene molecules,but also to EDA energy decomposition analysis.We calculate CCSD(T)/CBS for three simplified model systems that retain key structural features to verify the result.In the end,the?B97M-V method is the most suitable indeed.We use the B3LYP method to optimize the geometric structure of the metal phthalocyanine,and compare the total energy of the system in different electronic states.The most stable state is taken as the ground state,which eliminates the influence of the electronic state.Finally,we get the electronic state of the metal phthalocyanine ground state MPc(M=H₂,Ni,Zn)is a singlet state.MPc(M=Sc,Co,Cu)is a doublet state.MPc(M=Fe,Ti)is a triplet state.MPc(M=V,Mn)is a quartet state.MPc(M=Cr)is a quintet state.The ground state structure of MPc and the fullerene form the initial geometric structure at different action point.The ALMO-EDA energy decomposition results showed that the interaction energy between C₆₀,C₇₀,C₈₀ and MPc gradually increased.As the fullerene carbon cage gradually becomes larger,the carbon cage curvature decreases.At the same time,the contact surface of phthalocyanine and phthalocyanine increases,the polarization ability of the carbon cage increases,and the capacity to accept electrons also increases.The dispersion energy,polarization energy,and electron-transfer energy increase correspondingly.Of course,the greater the interaction energy,the greater deformation of metal phthalocyanines geometric structure.The intermolecular between fullerene and MPc(M=Ni,Cu,Zn,H₂)is mainly based on non-covalent interactions to achieve system stabilization.Dispersive energy is dominant in the system,followed by electrostatic energy.The contribution of electron-transfer and polarization energy is very less.The intermolecular interaction energy between fullerene and MPc(M=Sc,Ti,V,Mn)increases significantly.In addition to the main contributions of dispersion energy and electrostatic energy,the proportions of electron-transfer energy and polarization energy also increase.At the same time,the amount of electron-transfer has increased.Therefore,we believe that the non-covalent interaction and the?-back bond in this system.Complementary,the intermolecular interaction between fullerene and MPc(M=Fe,Co)is in a critical state.When C₆₀ or C₇₀ interaction with MPc(M=Fe,Co),it is a pure non-covalent interaction.When C₈₀ interaction with MPc(M=Fe,Co),it belongs to the co-existence of non-covalent interaction and?-back bond.According to the Mayer charge analysis results,all the fullerenes in the system exhibit electronic capacity properties.Furthermore,the amount of electron-transfer is always consistent with the electron-transfer energy.This paper studies the two dimensions of system energy and electronic structure changes.And it profoundly reveals the electronic structure and electron-transfer changes during the formation of the fullerene and MPc complex.Explore the nature of the interaction of free-base phthalocyanine/metal phthalocyanine and fullerene clearly.The summary of differences and regularity plays an important role in the experimental research and development of optoelectronic functional materials.