Though the photo-physical properties of free base porphyrin are attractive, there are still problems for the materials with weak and narrow range absorption of visible light. The unsymmetrical neo-confused porphyrin d...Though the photo-physical properties of free base porphyrin are attractive, there are still problems for the materials with weak and narrow range absorption of visible light. The unsymmetrical neo-confused porphyrin derivatives were introduced as novel materials for the improvement of photo-chemical and photo-physical properties. The density function theory（DFT）and time dependent density function theory（TDDFT） were applied to calculate the absorption spectrum of unsymmetrical neo-confused porphyrin（N-CP） and metal-coordinated N-CP in various solutions. The Ni and Zn coordinated neo-confused porphyrin dipole moment values are smaller than the values of prototype porphyrin（Pro P） and N–CP. According to the electrophilicity index ω, Ni coordinated N–CP（Ni–N–CP） is susceptible to the polarity of solvents, while the Zn coordinated derivative（Zn–N–CP） is more immune to the solvent environment. Unlike the Gouterman＇s four frontier orbital model of common porphyrin materials, the electron transitions of N–CPs and metalcoordinated N–CPs from H–2 or lower molecular orbitals also contribute to ultraviolet and visible absorption. Most of oscillator strength f values of Zn–N–CP are significantly higher than the values of Ni–N–CP, which reflects the higher absorption intensity of Q and Soret bands. The maximum wavelength at 702.2 nm in vacuum drew our attention to the novel material. The broad absorption range, intense red-shifted Q band and higher stability in solvents suggest that N–CPs, especially Zn–N–CP, can be one class of new candidate dye-sensitized materials.展开更多
文章基于新黎曼理论三和弦进行提出一个理论框架,以“平行”和“导音转换”两种仅涉及半音进行的三和弦变换架构六音系统和超六音系统,并通过在这一理论框架下分析瓦格纳、弗朗克、理查·施特劳斯等作曲家作品中的半音化和声,演示...文章基于新黎曼理论三和弦进行提出一个理论框架,以“平行”和“导音转换”两种仅涉及半音进行的三和弦变换架构六音系统和超六音系统,并通过在这一理论框架下分析瓦格纳、弗朗克、理查·施特劳斯等作曲家作品中的半音化和声,演示晚期浪漫主义音乐中三和弦在六音空间及自然音级空间中独特的进行方式。该理论框架的完整与自洽性、其与浪漫主义晚期创作实践的紧密联系,及其对游离于传统调性理论边缘的和声进行引发的思考,使该文成为新黎曼理论最具开创性的研究之一,以及该领域迄今引用量最高的文章(据web of science及谷歌学术数据)。展开更多
基金supported by the National Natural Science Foundation of China(Nos.21601025,21677029,21571025)Dalian Young Science and Technology Star Project(2017RQ156)
文摘Though the photo-physical properties of free base porphyrin are attractive, there are still problems for the materials with weak and narrow range absorption of visible light. The unsymmetrical neo-confused porphyrin derivatives were introduced as novel materials for the improvement of photo-chemical and photo-physical properties. The density function theory（DFT）and time dependent density function theory（TDDFT） were applied to calculate the absorption spectrum of unsymmetrical neo-confused porphyrin（N-CP） and metal-coordinated N-CP in various solutions. The Ni and Zn coordinated neo-confused porphyrin dipole moment values are smaller than the values of prototype porphyrin（Pro P） and N–CP. According to the electrophilicity index ω, Ni coordinated N–CP（Ni–N–CP） is susceptible to the polarity of solvents, while the Zn coordinated derivative（Zn–N–CP） is more immune to the solvent environment. Unlike the Gouterman＇s four frontier orbital model of common porphyrin materials, the electron transitions of N–CPs and metalcoordinated N–CPs from H–2 or lower molecular orbitals also contribute to ultraviolet and visible absorption. Most of oscillator strength f values of Zn–N–CP are significantly higher than the values of Ni–N–CP, which reflects the higher absorption intensity of Q and Soret bands. The maximum wavelength at 702.2 nm in vacuum drew our attention to the novel material. The broad absorption range, intense red-shifted Q band and higher stability in solvents suggest that N–CPs, especially Zn–N–CP, can be one class of new candidate dye-sensitized materials.
文摘文章基于新黎曼理论三和弦进行提出一个理论框架,以“平行”和“导音转换”两种仅涉及半音进行的三和弦变换架构六音系统和超六音系统,并通过在这一理论框架下分析瓦格纳、弗朗克、理查·施特劳斯等作曲家作品中的半音化和声,演示晚期浪漫主义音乐中三和弦在六音空间及自然音级空间中独特的进行方式。该理论框架的完整与自洽性、其与浪漫主义晚期创作实践的紧密联系,及其对游离于传统调性理论边缘的和声进行引发的思考,使该文成为新黎曼理论最具开创性的研究之一,以及该领域迄今引用量最高的文章(据web of science及谷歌学术数据)。
