A pyrrolidino[60]fullerene 1 with pyrrolidine group was synthesized and characterized. The UV-Vis spectra showed that the blue shift of absorption peaks was first observed when strong organic acids such as p-toluene s...A pyrrolidino[60]fullerene 1 with pyrrolidine group was synthesized and characterized. The UV-Vis spectra showed that the blue shift of absorption peaks was first observed when strong organic acids such as p-toluene sulfo-nic or trifluoroacetic acid were added to the solution of pyr-rolidino[60]fullerene 1 in dichloromethane. The results indicated that the pyrrolidino[60]fullerene derivatives without pyrrolidine group also possess the same phenomenon. Experiments and computation with the MOPAC 7.0 semi-empirical PM3 method demonstrated the reason that some energy gaps on [60]fullerene skeleton were increased because electronic charges on [60]fullerene framework transferred to pyrrolidine ring when strong organic acids were added into pyrrolidino[60]fullerene derivatives’ solution; as the result, the complexes could be formed and some absorption wavelengths blue shifted in the UV-Vis spectrum.展开更多
The O-2-CCT absorption spectra of bicomponent systems were measured. The influences of various organic compounds as well as the component concentration on the O-2-CCT formation ability were investigated. The results s...The O-2-CCT absorption spectra of bicomponent systems were measured. The influences of various organic compounds as well as the component concentration on the O-2-CCT formation ability were investigated. The results show that if the difference of O-2-CCT formation ability between the two components is rather large, such as the benzene/isopropyl ether system, only the O-2-CCT absorption of benzene appears, which arises from its higher O-2-CCT formation ability. If the difference of O-2-CCT formation ability is small, such as the isopropyl ether/ethanol system and the dioxane/isopropyl ether system, it is rather easy to form a dynamic equilibrium of two O-2-CCT between the two components, then only one absorption peak appears in the whole concentration range as a result of the repeated addition of the two kinds of O-2-CCT absorption. If the difference of O-2-CCT formation ability is in medium compared with the two cases above, such as the dioxane/ethanol system, there are two kinds of O-2-CCT absorption of dioxane and ethanol in the same system in the form of an equilibrium, then two absorption peaks can be detected in the middle concentration range as a result of the repeated addition of the two kinds of O-2-CCT absorption.展开更多
The properties of the TCNQ (7,7,8,8-tetracyanoquinodimethane) molecule, especially theproperties of its charge transfer complex and ion-pair compound with other molecules forelectro-optical switching and optical recor...The properties of the TCNQ (7,7,8,8-tetracyanoquinodimethane) molecule, especially theproperties of its charge transfer complex and ion-pair compound with other molecules forelectro-optical switching and optical recording, have attracted much attention since it wasfirst synthesized in 1962. When we prepared combined funtional materials using theTCNQ molecules and nanometer-sized particles in inverse micelle, we found that the inter-展开更多
The system of ZnPc-C60 ln speclal mixed organic solvents has been studled by UVVis, fluorescence and laser Raman spectra. The results prove the existence of a chargetransfer complex (CTC) by the lnteractlon between Zn...The system of ZnPc-C60 ln speclal mixed organic solvents has been studled by UVVis, fluorescence and laser Raman spectra. The results prove the existence of a chargetransfer complex (CTC) by the lnteractlon between ZnPc and C60 The molar ratio of ZnPc/C60 in CTC is 2: 1. The formation equilibrium constant(K) was determined at 25 C. Mea-surements of photovoltaic effect show that ZnPc-C60 CTC leads to a rernarkable enhancementof photosensitivity comparing to that of ZnPc.展开更多
The electronic structures and spectroscopic properties of [(4'-XC≡Ctrpy)PtCl]+(trpy = 2,2':6',2″-terpyridine; X = H (1),methyl (Me) (2),and phenyl (Ph) (3) were studied by the ab initio method. The struc...The electronic structures and spectroscopic properties of [(4'-XC≡Ctrpy)PtCl]+(trpy = 2,2':6',2″-terpyridine; X = H (1),methyl (Me) (2),and phenyl (Ph) (3) were studied by the ab initio method. The structures at the ground and excited state were optimized at the B3LYP and CIS levels,respectively. The absorption and emission spectra in the dichloromethane solution were obtained by using the TD-DFT (B3LYP) method associated with the PCM model. The molecular orbital energy of the HOMOs of 1-3 with the d(Pt),p(Cl),π(trpy),and π(XC≡C) character is sensitive to the substituents on the acetylide ligand,but that of the trpy-based LUMOs with the π*(trpy) character varies slightly. The lowest lying emission at 503 nm for 1 is mainly attributed to the 3ILCT perturbed by the 3MLCT and 3LLCT transitions,but that at 535 nm for 2,and that at 558 nm for 3 are mainly attributed to the 3LLCT perturbed by the 3ILCT and 3MLCT transitions. The different electron-donating ability of H,Me,and Ph is responsible for the differences in emission character. Moreover,the calculation results show that the phosphorescent color can be turned by adjusting the substituents. Both the lowest energy absorption and emission of 1―3 are red-shifted in the order of 1<2<3,consistent with the electron-donating of H<Me<Ph.展开更多
基金The work was supported by the National Natural Science Foundation of China (Grant No. 29871032) and the State MajorBasic Research Development Program (Grant No. G19990b4504).
文摘A pyrrolidino[60]fullerene 1 with pyrrolidine group was synthesized and characterized. The UV-Vis spectra showed that the blue shift of absorption peaks was first observed when strong organic acids such as p-toluene sulfo-nic or trifluoroacetic acid were added to the solution of pyr-rolidino[60]fullerene 1 in dichloromethane. The results indicated that the pyrrolidino[60]fullerene derivatives without pyrrolidine group also possess the same phenomenon. Experiments and computation with the MOPAC 7.0 semi-empirical PM3 method demonstrated the reason that some energy gaps on [60]fullerene skeleton were increased because electronic charges on [60]fullerene framework transferred to pyrrolidine ring when strong organic acids were added into pyrrolidino[60]fullerene derivatives’ solution; as the result, the complexes could be formed and some absorption wavelengths blue shifted in the UV-Vis spectrum.
文摘The O-2-CCT absorption spectra of bicomponent systems were measured. The influences of various organic compounds as well as the component concentration on the O-2-CCT formation ability were investigated. The results show that if the difference of O-2-CCT formation ability between the two components is rather large, such as the benzene/isopropyl ether system, only the O-2-CCT absorption of benzene appears, which arises from its higher O-2-CCT formation ability. If the difference of O-2-CCT formation ability is small, such as the isopropyl ether/ethanol system and the dioxane/isopropyl ether system, it is rather easy to form a dynamic equilibrium of two O-2-CCT between the two components, then only one absorption peak appears in the whole concentration range as a result of the repeated addition of the two kinds of O-2-CCT absorption. If the difference of O-2-CCT formation ability is in medium compared with the two cases above, such as the dioxane/ethanol system, there are two kinds of O-2-CCT absorption of dioxane and ethanol in the same system in the form of an equilibrium, then two absorption peaks can be detected in the middle concentration range as a result of the repeated addition of the two kinds of O-2-CCT absorption.
基金Project supported by the National Natural Science Foundation of China and the Foundation of the Third World Science Academy.
文摘The properties of the TCNQ (7,7,8,8-tetracyanoquinodimethane) molecule, especially theproperties of its charge transfer complex and ion-pair compound with other molecules forelectro-optical switching and optical recording, have attracted much attention since it wasfirst synthesized in 1962. When we prepared combined funtional materials using theTCNQ molecules and nanometer-sized particles in inverse micelle, we found that the inter-
文摘The system of ZnPc-C60 ln speclal mixed organic solvents has been studled by UVVis, fluorescence and laser Raman spectra. The results prove the existence of a chargetransfer complex (CTC) by the lnteractlon between ZnPc and C60 The molar ratio of ZnPc/C60 in CTC is 2: 1. The formation equilibrium constant(K) was determined at 25 C. Mea-surements of photovoltaic effect show that ZnPc-C60 CTC leads to a rernarkable enhancementof photosensitivity comparing to that of ZnPc.
基金Supported by the National Natural Science Foundation of China (Grant No. 20573042)China Postdoctoral Science Foundation (Grant No. 20080440149)
文摘The electronic structures and spectroscopic properties of [(4'-XC≡Ctrpy)PtCl]+(trpy = 2,2':6',2″-terpyridine; X = H (1),methyl (Me) (2),and phenyl (Ph) (3) were studied by the ab initio method. The structures at the ground and excited state were optimized at the B3LYP and CIS levels,respectively. The absorption and emission spectra in the dichloromethane solution were obtained by using the TD-DFT (B3LYP) method associated with the PCM model. The molecular orbital energy of the HOMOs of 1-3 with the d(Pt),p(Cl),π(trpy),and π(XC≡C) character is sensitive to the substituents on the acetylide ligand,but that of the trpy-based LUMOs with the π*(trpy) character varies slightly. The lowest lying emission at 503 nm for 1 is mainly attributed to the 3ILCT perturbed by the 3MLCT and 3LLCT transitions,but that at 535 nm for 2,and that at 558 nm for 3 are mainly attributed to the 3LLCT perturbed by the 3ILCT and 3MLCT transitions. The different electron-donating ability of H,Me,and Ph is responsible for the differences in emission character. Moreover,the calculation results show that the phosphorescent color can be turned by adjusting the substituents. Both the lowest energy absorption and emission of 1―3 are red-shifted in the order of 1<2<3,consistent with the electron-donating of H<Me<Ph.
