Diradical polycyclic hydrocarbons(PHs)have unique open-shell structures and interesting physical prop-erties.However,owing to high reactivity of unpaired electrons,such open-shell organic diradicaloids are usually les...Diradical polycyclic hydrocarbons(PHs)have unique open-shell structures and interesting physical prop-erties.However,owing to high reactivity of unpaired electrons,such open-shell organic diradicaloids are usually less stable than closed-shell systems,limiting their practical applications.In this study,we report P=O-attaching of diradical PHs as a new strategy to enhance their stability while maintaining diradi-cal properties.Three P=O-attached PHs containing the indeno[1,2-b]fluorene,fluoreno[3,2-b]fluorene and indeno[2,1-b]fluoreneπ-skeletons,respectively,were designed and synthesized.As theoretically and ex-perimentally proved,two of them have the relatively large diradical characters and open-shell singlet diradical nature.In comparison to their all-carbon analogues,the attached electron-withdrawing P=O groups endow them with much lower LUMO/HOMO energy levels but preserved magnetic activities and physical properties,such as thermally accessible triplet species and multi-redox ability.Moreover,the P=O groups effectively decrease their oxidation activities and thereby lead to their remarkably excellent ambient stabilities.Thus,this P=O-attaching strategy will be applicable to other diradical PH systems and may promote the generation of stable organic diradicaloids for radical chemistry and materials.展开更多
The k-epsilon model was applied to establish the mathematical model of vertical round buoyant jet discharging into confined depth, and it was solved using the Hybrid Finite Analytic Method (HFAM). The numerical predic...The k-epsilon model was applied to establish the mathematical model of vertical round buoyant jet discharging into confined depth, and it was solved using the Hybrid Finite Analytic Method (HFAM). The numerical predictions demonstrate two generic flow patterns for different jet discharge and environmental parameters: (ⅰ)a stable buoyant flow discharge with the mixed fluid leaving the near-field warm in a surface warm water layer; (ⅱ)an unstable buoyant flow discharge with recirculation and re-entrainment of warm water in the near field. Furthermore, the mixing characters of vertical round buoyant jet were numerically predicted. Both the stability criterion and numerical predictions of bulk dilutions are in excellent agreement with Lee and Jirka's experiments and theory.展开更多
基金supported by Jilin Scientific and Technological Development Program(Nos.20220101054JC,20220201085GX)National Natural Science Foundation of China(Nos.22175074,52373182).
文摘Diradical polycyclic hydrocarbons(PHs)have unique open-shell structures and interesting physical prop-erties.However,owing to high reactivity of unpaired electrons,such open-shell organic diradicaloids are usually less stable than closed-shell systems,limiting their practical applications.In this study,we report P=O-attaching of diradical PHs as a new strategy to enhance their stability while maintaining diradi-cal properties.Three P=O-attached PHs containing the indeno[1,2-b]fluorene,fluoreno[3,2-b]fluorene and indeno[2,1-b]fluoreneπ-skeletons,respectively,were designed and synthesized.As theoretically and ex-perimentally proved,two of them have the relatively large diradical characters and open-shell singlet diradical nature.In comparison to their all-carbon analogues,the attached electron-withdrawing P=O groups endow them with much lower LUMO/HOMO energy levels but preserved magnetic activities and physical properties,such as thermally accessible triplet species and multi-redox ability.Moreover,the P=O groups effectively decrease their oxidation activities and thereby lead to their remarkably excellent ambient stabilities.Thus,this P=O-attaching strategy will be applicable to other diradical PH systems and may promote the generation of stable organic diradicaloids for radical chemistry and materials.
文摘The k-epsilon model was applied to establish the mathematical model of vertical round buoyant jet discharging into confined depth, and it was solved using the Hybrid Finite Analytic Method (HFAM). The numerical predictions demonstrate two generic flow patterns for different jet discharge and environmental parameters: (ⅰ)a stable buoyant flow discharge with the mixed fluid leaving the near-field warm in a surface warm water layer; (ⅱ)an unstable buoyant flow discharge with recirculation and re-entrainment of warm water in the near field. Furthermore, the mixing characters of vertical round buoyant jet were numerically predicted. Both the stability criterion and numerical predictions of bulk dilutions are in excellent agreement with Lee and Jirka's experiments and theory.
