Study On The Second-order Nonlinear Optical Of Corrole Derivatives And The Oxygen Transfer Reaction Of Mnagnese-oxo Corrole

With the emergency of the laser,the human gradually find luminescent material isnot only the linear function relation with the existed electromagnetic field,but also theexistence of the nonlinear function relation.From the1960s,since the phenomena ofnonlinear optics(NLO) was found,NLO has rapidly developed.And because theorganic NLO materials has a very short optical response time,chemical modificationand chemical damage threshold is higher and so on,the organic light-emittingmaterials get rapid development.Now the key issue is how to improve the NLOproperties of organic chromophore,the focus of the NLO materials is the asymmetricstrution.And the corrole has this struction,and relate to the porphyrinmolecules,corrole ring reduces a c atom,but NLO of corrole is more significant relateto the reports,so the corrole will provide a good platform for the modification oforganic NLO.One of the method of improving molecular nonlinear performance is the push-pullelectronic system, but the positions of substituent of corrode molecules there are twomain types: meso-and β-，so we design two kinds of molecules, one kind studies theinfluence of the m-,o-,p-of the benzene of the ten position in the corrole ring, the otheris four molecules of the β position of the corrole.At the same time,the accumulationmode of the molecules can significantly affect the NLO performance,therefore, wehave designed three kinds of packing way-H, J, X。We design the three seriesmodels,use Gaussion03software,and at the level of6-31G*use the way of quantumchemistry to optimize the molecular geometry,then use the way of ZINDO tocalculate electronic spectra,and use ZINDO/SOS combined with the finited(FF) tocalculate the first-order molecules’ hyperpolarization rate coefficient βHRSin order tocomprehensive study the influence of the substituents in the position of meso-and β-of the corrole.Study find in the position of corrole meso-,the relationship betweenthe size of the NLO properties is:m->O->P-,besides two-level component changingthe most. The reasons of substituent of m-having the most NLO properties is themolecular transition dipole distance.But the energy between HOMO and LUMO decreases,and it is not consistent with the two-level component.As a result,whendiscussing the influence of the substituent,three-level component should beconsidered at the same time.In the position of βof corrole,study find that thesubstituents have a great influence on the NLO properties of corrole compounds,andmainly affects two-level component,besides can increase the NLO properties of thedifferent level.When the positon of the β in the molecule didn’t replace, βHRSis108.73×10-30esu,but when replaced,the biggest number is156.10×10-30esu,it can beincreased by50%,at the same time,these substituents mainly influence betweenground and excited state transition dipole and the different excited dipole.Besides, wealso studied the porphyrin molecular accumulation effect on the properties ofmolecular NLO，the βHRSof accumulation modes are620×10-30esu，426.2×10-30esuand63×10-30esu,we can known that the NLO property of X-accumulation andJ-accumulation are better than H-accumulation, this is because in the H-gathered,accidentally interelectrode of mutual influence,it will lead to split the energy of theaccumulation, and the stability excited states after splitting on optical is prohibited.When molecules from the ground state transit to the excited state, relax and return tothe lowest excited state, however, the excited state transition is prevented,it can notspontaneous transition to ground state, therefore, this molecular accumulation modeoften leads to aggregate’s NLO performance degradation. So, in the molecularaggregation, we should decrease H gathered, and should improve X-ray gatheredtrend, which increases the NLO properties of the material.At the same time,we study the Mn-O OXO catalytic oxidation ability to thesubstituents.Using B3LYP basis set to MnⅤ-O corrole compounds geometricstructures optimization,and on the basis of these,the influence of the substituent onMnⅤ-O corrole compounds transfer the O atom to dimethyl sulfide are studied. Thecalculation results show that corrole and high metal MnⅤby d-π conjugate, canimprove the stability of high metal Mn, and prompt MnⅤ-O corrole complexes with18electronic stability structure. Because of the five fluorinated phenyl strongelectron-withdrawing substituent effect, it can lead to MnⅤ-O corrole molecular’scharge significant change, and affect the molecular orbitals, which influences the course of the OAT. According to a study,the fluorine substituent at the βposition ofthe corrole can be even more significant influence of molecular structure and theenergy difference between products and reactants, promoting the oxygen transferbetween compounds. In the reaction path of singlet，the reaction energy barrier can beup to20kcal/mol, but in triplet reaction path, the energy barriers can be greatlyreduced, this shows that in the process of reaction, the reactants may change the spinstates, thus it can promote the OAT reaction. Studies have shown that when MnⅤ-Ocorrode compounds was replaced by the electron-withdrawing substituents,it isbeneficial to the oxygen transfer, with the consistent of the experimental results innonpolar solvent, it shows that calculation by DFT can study the effects of singlefactors on the reaction,and it is advantageous to the reaction to the nature of research.