I have been working on people-topeople friendship between China and Romania for 46 years,ever since my government-sponsored overseas study in 1973.I have studied and worked in Romania for more than20 years.My work in ...I have been working on people-topeople friendship between China and Romania for 46 years,ever since my government-sponsored overseas study in 1973.I have studied and worked in Romania for more than20 years.My work in China has also been closely related to relations with Romania.展开更多
Hammett constants,a popular tool for predicting substitution effects on chemical reactivity and catalytic activity,the binding affinity of drugs and the spin-crossover(SCO)behavior of metal complexes,are frequently cr...Hammett constants,a popular tool for predicting substitution effects on chemical reactivity and catalytic activity,the binding affinity of drugs and the spin-crossover(SCO)behavior of metal complexes,are frequently criticized.Among others,they define the acetoxy group as electron-withdrawing(EWG),although it activates electrophilic substitution in the benzene ring as an electron donor(EDG).We argue that SCO compounds provide an excellent platform for reevaluating Hammett constants,with the SCO midpoint temperature as a quantitative measure of even subtle changes in organic ligands.For a new series of iron(Ⅱ)complexes of bis(pyrazol-3-yl)pyridines(3-bpp),this measure showed a contradictory increase induced by both EWGs and EDGs.Yet,it correlated linearly with NMR chemical shifts,metal-ligand bond lengths and energies.Together,these correlations yielded Hammett constants that correctly identified the acetoxy group as an EDG,among others.The new constants allowed us not only to explain the SCO behaviour of metal complexes with 3-bpp and other popular families of N-donor ligands but also to predict the SCO midpoint temperature with high accuracy.Beyond the SCO realm,they were extended to rationalize the outcomes of Diels-Alder and polymerization reactions.By using metal-ligand bond lengths routinely measured for coordination compounds,Hammett constants can be further‘refined’to help design new,more efficient catalysts,drugs and materials for advanced applications in quantum technologies and(bio)sensing,energy conversion and smart/self-healing coatings.展开更多
Application of the Marcus cross relation(MCR)to determine electron transfer rate constants is well documented.In addition to outer sphere reduction/oxidation of O_(2)/O_(2)^(·−),the MCR is also applicable for pro...Application of the Marcus cross relation(MCR)to determine electron transfer rate constants is well documented.In addition to outer sphere reduction/oxidation of O_(2)/O_(2)^(·−),the MCR is also applicable for proton transfer(PT),proton-coupled electron transfer(PCET),and hydride transfer rate constants.A question this report aims to address is whether or not the MCR can predict rate constants for inner sphere electron transfer(ISET)reactions between iron complexes and O_(2).By including the iron–superoxide bond dissociation energy(BDFEFe–O_(2))into the MCR equilibrium constant,close values to experimental inner sphere O_(2) reductions are estimated.This insight of including the iron–superoxide binding energy as a design element for the development of synthetic oxygenases is considered.展开更多
文摘I have been working on people-topeople friendship between China and Romania for 46 years,ever since my government-sponsored overseas study in 1973.I have studied and worked in Romania for more than20 years.My work in China has also been closely related to relations with Romania.
基金supported by the Russian Science Foundation(project 24-73-00165)the equipment of the Center for Collective Use of INEOS RAS with support from the Ministry of Science and Higher Education of the Russian Federation(contract/agreement supported by the Russian Science Foundation(project 24-73-00165)+1 种基金performed using the equipment of the Center for Collective Use of INEOS RAS with support from the Ministry of Science and Higher Education of the Russian Federation(contract/agreement no.075-00276-25-00)the support of the Spanish Ministry of Science(grant BG22/00039).
文摘Hammett constants,a popular tool for predicting substitution effects on chemical reactivity and catalytic activity,the binding affinity of drugs and the spin-crossover(SCO)behavior of metal complexes,are frequently criticized.Among others,they define the acetoxy group as electron-withdrawing(EWG),although it activates electrophilic substitution in the benzene ring as an electron donor(EDG).We argue that SCO compounds provide an excellent platform for reevaluating Hammett constants,with the SCO midpoint temperature as a quantitative measure of even subtle changes in organic ligands.For a new series of iron(Ⅱ)complexes of bis(pyrazol-3-yl)pyridines(3-bpp),this measure showed a contradictory increase induced by both EWGs and EDGs.Yet,it correlated linearly with NMR chemical shifts,metal-ligand bond lengths and energies.Together,these correlations yielded Hammett constants that correctly identified the acetoxy group as an EDG,among others.The new constants allowed us not only to explain the SCO behaviour of metal complexes with 3-bpp and other popular families of N-donor ligands but also to predict the SCO midpoint temperature with high accuracy.Beyond the SCO realm,they were extended to rationalize the outcomes of Diels-Alder and polymerization reactions.By using metal-ligand bond lengths routinely measured for coordination compounds,Hammett constants can be further‘refined’to help design new,more efficient catalysts,drugs and materials for advanced applications in quantum technologies and(bio)sensing,energy conversion and smart/self-healing coatings.
文摘Application of the Marcus cross relation(MCR)to determine electron transfer rate constants is well documented.In addition to outer sphere reduction/oxidation of O_(2)/O_(2)^(·−),the MCR is also applicable for proton transfer(PT),proton-coupled electron transfer(PCET),and hydride transfer rate constants.A question this report aims to address is whether or not the MCR can predict rate constants for inner sphere electron transfer(ISET)reactions between iron complexes and O_(2).By including the iron–superoxide bond dissociation energy(BDFEFe–O_(2))into the MCR equilibrium constant,close values to experimental inner sphere O_(2) reductions are estimated.This insight of including the iron–superoxide binding energy as a design element for the development of synthetic oxygenases is considered.
