Acridinium dyes have been broadly used as photocatalysts,but it remains synthetically challenging to fine-tune their catalytic performance by functionalization of their structural cores.Acridinium photocatalysts are u...Acridinium dyes have been broadly used as photocatalysts,but it remains synthetically challenging to fine-tune their catalytic performance by functionalization of their structural cores.Acridinium photocatalysts are usually prepared through de novo synthesis,which involves difficult steps and requires sensitive organometallic reagents.展开更多
Hybrid quantum mechanics/molecular mechanics calculations were performed to elucidate how[Mn^(Ⅲ)porphyrin]^(+X−)-based metal-organic frameworks(MOFs)catalyze the[2+1]cycloisomerization of enynes and why zwitterionic ...Hybrid quantum mechanics/molecular mechanics calculations were performed to elucidate how[Mn^(Ⅲ)porphyrin]^(+X−)-based metal-organic frameworks(MOFs)catalyze the[2+1]cycloisomerization of enynes and why zwitterionic MOFs exhibit strong activity in Lewis acid catalysis.The calculations showed that zwitterionic MOFs have a“pure cationic active center”leading to a concerted nucleophilic attack pathway with lower barriers.In contrast,metals with coordinating anions have reduced electrophilicity,resulting in a stepwise radical-type pathway with much higher barriers.Further calculations showed the nature of catalysis was strongly depended on the charge on the anion ligand.A good linear relationship between the NPA charge and barrier was found,and verified by 73 anions with small derivations,which presents a universal adaptive character for various coordinated anions.展开更多
基金The authors acknowledge the financial support of this research from NSFC(no.21672178,21971213)MOST(no.2016YFA0204100)+2 种基金the National Postdoctoral Program for Innovative Talents(no.BX201700141)China Postdoctoral Science Foundation(no.2018M630730)Fundamental Research Funds for the Central Universities.
文摘Acridinium dyes have been broadly used as photocatalysts,but it remains synthetically challenging to fine-tune their catalytic performance by functionalization of their structural cores.Acridinium photocatalysts are usually prepared through de novo synthesis,which involves difficult steps and requires sensitive organometallic reagents.
基金supported by the National Natural Science Foundation of China (Nos. 21822303 21772020 22173083)Program for Science Technology Innovation Talents in Universities of Henan Province (No. 20HASTIT004)the support from the Henan Province Supercomputing Center
文摘Hybrid quantum mechanics/molecular mechanics calculations were performed to elucidate how[Mn^(Ⅲ)porphyrin]^(+X−)-based metal-organic frameworks(MOFs)catalyze the[2+1]cycloisomerization of enynes and why zwitterionic MOFs exhibit strong activity in Lewis acid catalysis.The calculations showed that zwitterionic MOFs have a“pure cationic active center”leading to a concerted nucleophilic attack pathway with lower barriers.In contrast,metals with coordinating anions have reduced electrophilicity,resulting in a stepwise radical-type pathway with much higher barriers.Further calculations showed the nature of catalysis was strongly depended on the charge on the anion ligand.A good linear relationship between the NPA charge and barrier was found,and verified by 73 anions with small derivations,which presents a universal adaptive character for various coordinated anions.
