Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer （MLCT） in ruthenium（II） ammine compl...Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer （MLCT） in ruthenium（II） ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os（bpy）2（p0p）Cl （＂Osp0p＂： bpy=2,2-bipyrldyl; p0p=4,4＇- bipyridyl） and the ligand-to-ligand charge transfer （LLCT） in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.展开更多
To elucidate the nature of low-lying triplet states and the effect of ligand modifica- tions on the excited-state properties of functional cationic iridium complexes, the solvent- dependent excited-state dynamics of t...To elucidate the nature of low-lying triplet states and the effect of ligand modifica- tions on the excited-state properties of functional cationic iridium complexes, the solvent- dependent excited-state dynamics of two phosphorescent cationic iridium（Ⅲ） complexes, namely [Ir（dph-oxd）2（bpy）]PF6 （1） and [Ir（dph-oxd）2（pzpy）]Pf6 （2）, were investigated by femtosecond and nanosecond transient absorption spectroscopy. Upon photoexcitation to the metal-to-ligand charge-transfer （MLCT） states, the excited-state dynamics shows a rapid process （τ-=0.7-3 ps） for the formation of solvent stabilized 3MLCT states, which significantly depends on the solvent polarity for both 1 and 2. Sequentially, a relatively slow process assigned to the vibrational cooling/geometrical relaxation and a long-lived phospho- rescent emissive state is identified. Due to the different excited-state electronic structures regulated by ancillary ligands, the solvation-induced stabilization of the 3MLCT state in 1 is faster than that in 2. The present results provide a better sight of excited-state relaxation dynamics of ligand-related iridium（Ⅲ） complexes and solvation effects on triplet manifolds.展开更多
A novel 3 D bismuth-organic framework(called Bi-TBAPy) single crystal was synthesized by employing 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H4TBAPy) as an organic linker. The study demonstrates that the Bi-TBAPy not onl...A novel 3 D bismuth-organic framework(called Bi-TBAPy) single crystal was synthesized by employing 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H4TBAPy) as an organic linker. The study demonstrates that the Bi-TBAPy not only possesses good chemical stability and suitable band edge positions for promising photocatalytic H2 evolution, but it also exhibits a typical ligand-to-metal charge transfer for favorable charge separation. The photocatalytic H2 evolution rates on the as-obtained Bi-TBAPy with different cocatalysts modified were examined with triethanolamine as the sacrificial reagent. Based on this, the hydrogen evolution rate of 140 μmol h-1 g-1 was obtained on the optimized sample with a loading of 2 wt% Pt as a cocatalyst. To the best of our knowledge, this is the first bismuth-based metal-organic framework(MOF) that functions as an effective photocatalyst for photocatalytic water reduction. Our study not only adds a new member to the family of photocatalyst materials, but also reveals the importance of cocatalyst modification in improving photocatalytic activity of MOFs.展开更多
The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order...The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order nonlinear optical （NLO） responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer （ILCT）, while the complexes in series b exhibit metal-to-ligand charge transfer （MLCT） and lig- and-to-ligand charge transfer （LLCT） transition at relatively low-energy absorptions.展开更多
基金This work was supported by National Natural Science Foundation of China （No.10505001, No.10875055, and No.10874234） and the Educational Department of Liaoning Province （No.2008228）.
文摘Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer （MLCT） in ruthenium（II） ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os（bpy）2（p0p）Cl （＂Osp0p＂： bpy=2,2-bipyrldyl; p0p=4,4＇- bipyridyl） and the ligand-to-ligand charge transfer （LLCT） in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.
文摘To elucidate the nature of low-lying triplet states and the effect of ligand modifica- tions on the excited-state properties of functional cationic iridium complexes, the solvent- dependent excited-state dynamics of two phosphorescent cationic iridium（Ⅲ） complexes, namely [Ir（dph-oxd）2（bpy）]PF6 （1） and [Ir（dph-oxd）2（pzpy）]Pf6 （2）, were investigated by femtosecond and nanosecond transient absorption spectroscopy. Upon photoexcitation to the metal-to-ligand charge-transfer （MLCT） states, the excited-state dynamics shows a rapid process （τ-=0.7-3 ps） for the formation of solvent stabilized 3MLCT states, which significantly depends on the solvent polarity for both 1 and 2. Sequentially, a relatively slow process assigned to the vibrational cooling/geometrical relaxation and a long-lived phospho- rescent emissive state is identified. Due to the different excited-state electronic structures regulated by ancillary ligands, the solvation-induced stabilization of the 3MLCT state in 1 is faster than that in 2. The present results provide a better sight of excited-state relaxation dynamics of ligand-related iridium（Ⅲ） complexes and solvation effects on triplet manifolds.
基金supported by the National Natural Science Foundation of China(21633009,21522306,21633010)DICP&QIBEBT(UN201805)the Dalian Science Foundation for Distinguished Young Scholars(2017RJ02)~~
文摘A novel 3 D bismuth-organic framework(called Bi-TBAPy) single crystal was synthesized by employing 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H4TBAPy) as an organic linker. The study demonstrates that the Bi-TBAPy not only possesses good chemical stability and suitable band edge positions for promising photocatalytic H2 evolution, but it also exhibits a typical ligand-to-metal charge transfer for favorable charge separation. The photocatalytic H2 evolution rates on the as-obtained Bi-TBAPy with different cocatalysts modified were examined with triethanolamine as the sacrificial reagent. Based on this, the hydrogen evolution rate of 140 μmol h-1 g-1 was obtained on the optimized sample with a loading of 2 wt% Pt as a cocatalyst. To the best of our knowledge, this is the first bismuth-based metal-organic framework(MOF) that functions as an effective photocatalyst for photocatalytic water reduction. Our study not only adds a new member to the family of photocatalyst materials, but also reveals the importance of cocatalyst modification in improving photocatalytic activity of MOFs.
基金supported by the National Natural Science Foundation of China (20873017)the Natural Science Foundation of Jilin Province (20101154)
文摘The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order nonlinear optical （NLO） responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer （ILCT）, while the complexes in series b exhibit metal-to-ligand charge transfer （MLCT） and lig- and-to-ligand charge transfer （LLCT） transition at relatively low-energy absorptions.
