The photochemical reaction of magnesium tetraphenyl porphyrin（MgTPP） with sulfur dioxide（SO_2） was investigated in dichloromethane（CH_2Cl_2） by steady-state fluorescence,UV-vis absorption,MS,and XRD spectroscopi...The photochemical reaction of magnesium tetraphenyl porphyrin（MgTPP） with sulfur dioxide（SO_2） was investigated in dichloromethane（CH_2Cl_2） by steady-state fluorescence,UV-vis absorption,MS,and XRD spectroscopic techniques.These spectra showed that under irradiation MgTPP reacted with SO_2 to form 1：1 molecular adduct at first step.During the process of keeping irradiation and maintaining the flow of SO_2,SO_2 was reduced into S^（2-） by MgTPP and the results were detected using MS and XRD techniques.Understanding the photochemical reaction of MgTPP with SO_2 is of key interest in elucidating fundamental photochemical reaction mechanisms associated with this class of chlorophyll in the presence of SO_2.展开更多
The photochemical reaction of magnesium tetraphenyl porphyrin （MgTPP） with O2 was studied in CH2Cl2 by steady-state fluorescence, UV-vis absorption, FTIR and MALDI-TOF MS measurements. These spectra indicate that O2...The photochemical reaction of magnesium tetraphenyl porphyrin （MgTPP） with O2 was studied in CH2Cl2 by steady-state fluorescence, UV-vis absorption, FTIR and MALDI-TOF MS measurements. These spectra indicate that O2 can react with MgTPP excited by irradiation, forming the stable 1：1 coordinated adduct of MgTPP-O2. In the adduct, the oxygen atoms of O2 may insert in the Mg-N bonds in MgTPP and bind with the nitrogen atoms of MgTPP to form N-O-Mg bonds.展开更多
The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2...The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenyl porphyrin （5） and its Ni （Ⅱ） （6）, Cu （Ⅱ） （7）, Zn （Ⅱ） （8） complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 （70%）, 6 （34%）, 7 （54%） and 8 （50%）, the corresponding 2-（2-naphythoxy）-5, 10,15,20-tetraphenylporphyrin （9）, and its Ni （Ⅱ） （10）, Cu （Ⅱ） （11）, Zn （Ⅱ） （12） complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.展开更多
基金financed by Yongfeng Boyuan Industry Co.,Ltd.,(Jiangxi province,China).Thanks to Professor Wenting Hua and Professor Hongcheng Gao(Peking University,China) for their suggestions on the photochemical interaction mechanism of MgTPP with SO_2.
文摘The photochemical reaction of magnesium tetraphenyl porphyrin（MgTPP） with sulfur dioxide（SO_2） was investigated in dichloromethane（CH_2Cl_2） by steady-state fluorescence,UV-vis absorption,MS,and XRD spectroscopic techniques.These spectra showed that under irradiation MgTPP reacted with SO_2 to form 1：1 molecular adduct at first step.During the process of keeping irradiation and maintaining the flow of SO_2,SO_2 was reduced into S^（2-） by MgTPP and the results were detected using MS and XRD techniques.Understanding the photochemical reaction of MgTPP with SO_2 is of key interest in elucidating fundamental photochemical reaction mechanisms associated with this class of chlorophyll in the presence of SO_2.
基金Jiangxi Boyuan Industry Co.Ltd.(Jiangxi Province,China).
文摘The photochemical reaction of magnesium tetraphenyl porphyrin （MgTPP） with O2 was studied in CH2Cl2 by steady-state fluorescence, UV-vis absorption, FTIR and MALDI-TOF MS measurements. These spectra indicate that O2 can react with MgTPP excited by irradiation, forming the stable 1：1 coordinated adduct of MgTPP-O2. In the adduct, the oxygen atoms of O2 may insert in the Mg-N bonds in MgTPP and bind with the nitrogen atoms of MgTPP to form N-O-Mg bonds.
基金Project supported by the National Natural Science Foundation of China （No. 29872033）.
文摘The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenyl porphyrin （5） and its Ni （Ⅱ） （6）, Cu （Ⅱ） （7）, Zn （Ⅱ） （8） complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 （70%）, 6 （34%）, 7 （54%） and 8 （50%）, the corresponding 2-（2-naphythoxy）-5, 10,15,20-tetraphenylporphyrin （9）, and its Ni （Ⅱ） （10）, Cu （Ⅱ） （11）, Zn （Ⅱ） （12） complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.
