Chiral bis-corrole 1 and 2 were prepared by reaction of （s）-2,2′-bis（bromomethyl）-1, 1′-binaphthyl and 10-（4-hydroxylphenyl）- 5,15-bis（pentafluorophenyl）corrole or 10-（3-hydroxylphenyl）-5,15-bis（pentafluo...Chiral bis-corrole 1 and 2 were prepared by reaction of （s）-2,2′-bis（bromomethyl）-1, 1′-binaphthyl and 10-（4-hydroxylphenyl）- 5,15-bis（pentafluorophenyl）corrole or 10-（3-hydroxylphenyl）-5,15-bis（pentafluorophenyl）corrole in DMF at 60 ℃ in the presence of anhydrous K2CO3 with an isolated yield -8%. Both 1 and 2 exhibit unsymmetrical induced circular dichroism （ICD） in the soret band with positive exciton chirality.展开更多
The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/P...The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/PM3 method based on the RHF/6-31G （TPC and TPP） or semiempirical PM3 （1, 2, 3, 4） optimized geometries. Calculation results showed TPC and TPP have C1 and D2h symmetry, respectively when N-H protons are localized on the nitrogen atoms. TPC is the second-order NLO active chromophore due to the cancellation of centrosymmetrical structure and its first hyperpolarizability β increases to 11.524×10^-30 esu. Under electrical dipole approximation, βvalues of bis-corroles 1, 2, 3 and 4 vary from 9.831×10^-30 to 14.221×10^-30 esu, and no much improvement in the first hyperpolarizability was observed as compared to TPC monomer.However, β values of bis-corroles 1, 2, 3 and 4 are improved by about 4 times as compared to their bis-porphyrin counterparts. The analysis of β components indicates that β of this kind of bis-corroles is mainly contributed from its radial component βr. With the variation of amino acid side chains, βHRS, β,βxyz, βr and βa of bis-corroles change remarkably. Chiral L-amino acid bridged bis-corroles 2, 3 and 4 have a right-handed helix structure, and their chiral component βxyz matches βxyz ∝ r^2 ζ/L^4 （helix parameters）, showing the second-order chiral NLO response of these bis-corroles could be described by one-electron helical model theory. It was found that the radial component βr of chiral helix bis-corroles also matches βr ∝ r^2 ζ/L^4.展开更多
Three binuclear metal (M=Co,Fe,Mn) xanthine bridged bis-corrole complexes were synthesized and investigated as electrocatalysts for the hydrogen evolution reaction (HER).All the prepared metal bis-corrole catalysts ex...Three binuclear metal (M=Co,Fe,Mn) xanthine bridged bis-corrole complexes were synthesized and investigated as electrocatalysts for the hydrogen evolution reaction (HER).All the prepared metal bis-corrole catalysts exhibited good HER performance when using acetic acid (AcOH);trifluoroacetic acid (TFA);p-toluenesulfonic acid (TsOH) as proton sources.The catalytic HER activities followed an order of Co bis-corrole (1)> Fe bis-corrole (2)> Mn bis-corrole (3);complex 1 exhibited a significantly lower overpotential at -270 mV (in TsOH).Furthermore,complex 1 may go EECC and EECEC pathways in organic solvents (E: electron transfer step,C: proton coupling);exhibit an HER activity with a turnover frequency (TOF) of 85 h^(-1) and a Faraday efficiency of 94% when using water as proton source.展开更多
基金supported by Natural Science Foundation of China(Nos.20771039 and 20572027),Research GrantCouncil of Hong Kong.
文摘Chiral bis-corrole 1 and 2 were prepared by reaction of （s）-2,2′-bis（bromomethyl）-1, 1′-binaphthyl and 10-（4-hydroxylphenyl）- 5,15-bis（pentafluorophenyl）corrole or 10-（3-hydroxylphenyl）-5,15-bis（pentafluorophenyl）corrole in DMF at 60 ℃ in the presence of anhydrous K2CO3 with an isolated yield -8%. Both 1 and 2 exhibit unsymmetrical induced circular dichroism （ICD） in the soret band with positive exciton chirality.
基金Supported by the NNSFC (20476034), Research Grants Council of Hongkong and SRF for ROCS, State Education Ministry
文摘The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/PM3 method based on the RHF/6-31G （TPC and TPP） or semiempirical PM3 （1, 2, 3, 4） optimized geometries. Calculation results showed TPC and TPP have C1 and D2h symmetry, respectively when N-H protons are localized on the nitrogen atoms. TPC is the second-order NLO active chromophore due to the cancellation of centrosymmetrical structure and its first hyperpolarizability β increases to 11.524×10^-30 esu. Under electrical dipole approximation, βvalues of bis-corroles 1, 2, 3 and 4 vary from 9.831×10^-30 to 14.221×10^-30 esu, and no much improvement in the first hyperpolarizability was observed as compared to TPC monomer.However, β values of bis-corroles 1, 2, 3 and 4 are improved by about 4 times as compared to their bis-porphyrin counterparts. The analysis of β components indicates that β of this kind of bis-corroles is mainly contributed from its radial component βr. With the variation of amino acid side chains, βHRS, β,βxyz, βr and βa of bis-corroles change remarkably. Chiral L-amino acid bridged bis-corroles 2, 3 and 4 have a right-handed helix structure, and their chiral component βxyz matches βxyz ∝ r^2 ζ/L^4 （helix parameters）, showing the second-order chiral NLO response of these bis-corroles could be described by one-electron helical model theory. It was found that the radial component βr of chiral helix bis-corroles also matches βr ∝ r^2 ζ/L^4.
基金supported by the National Natural Science Foundation of China(Nos.21671068,22005052)the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology,China(No.FC202211).
文摘Three binuclear metal (M=Co,Fe,Mn) xanthine bridged bis-corrole complexes were synthesized and investigated as electrocatalysts for the hydrogen evolution reaction (HER).All the prepared metal bis-corrole catalysts exhibited good HER performance when using acetic acid (AcOH);trifluoroacetic acid (TFA);p-toluenesulfonic acid (TsOH) as proton sources.The catalytic HER activities followed an order of Co bis-corrole (1)> Fe bis-corrole (2)> Mn bis-corrole (3);complex 1 exhibited a significantly lower overpotential at -270 mV (in TsOH).Furthermore,complex 1 may go EECC and EECEC pathways in organic solvents (E: electron transfer step,C: proton coupling);exhibit an HER activity with a turnover frequency (TOF) of 85 h^(-1) and a Faraday efficiency of 94% when using water as proton source.
