期刊：
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY,2024年321:124704 ISSN：1386-1425
通讯作者：
Liu, SH;Zhang, J;Ou, YP
作者机构：
[Peng, Zhen; Liu, Sheng Hua; Liu, SH] Cent China Normal Univ, State Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Zhang, Jing; Deng, Shuangling; Lin, Yiling; Zhang, J] Southern Med Univ, Nanfang Hosp, Dept Lab Med, Guangzhou 510515, Peoples R China.;[Ou, Ya-Ping; Ou, YP; Liu, Zhenji] Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Prov Key Lab Funct Met Organ Cpds, Hengyang 421008, Peoples R China.;[Ou, Ya-Ping; Xia, Yonglin] Hengyang Normal Univ, Nanyue Coll, Hengyang 421001, Hunan, Peoples R China.
通讯机构：
[Ou, YP ] H;[Liu, SH ] C;[Zhang, J ] S;Cent China Normal Univ, State Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Southern Med Univ, Nanfang Hosp, Dept Lab Med, Guangzhou 510515, Peoples R China.
摘要：
The thiophene- and pyrrole-fused heterocyclic compounds have garnered significant interest for their distinctive electron-rich characteristics and notable optoelectronic properties. However, the construction of high-performance systems within this class is of great challenge. Herein, we develop a series of novel dithieno[3,2-b:2',3'-d] pyrrole (DTP) and tetrathieno[3,2-b:2',3'-d] pyrrole (TTP) bridged arylamine compounds (DTP-C(4), DTP-C(12), DTP-C(4)-Fc, TTP-C(4)-OMe, TTP-C(4), and TTP-C(12)) with varying carbon chain lengths. The pertinent experimental results reveal that this series of compounds undergo completely reversible multistep redox processes. Notably, TTP-bridged compounds TTP-C(4) and TTP-C(12) exhibit impressive multistep near-infrared (NIR) absorption alterations with notable color changes and electroluminescent behaviors, which are mainly attributed to the charge transfer transitions from terminal arylamine units to central bridges, as supported by theoretical calculations. Additionally, compound DTP-C(4) demonstrates the ability to visually identify gram-positive and gram-negative bacteria. Therefore, this work suggests the promising electroresponsive nature of compounds TTP-C(4) and TTP-C(12), positioning them as excellent materials for various applications. It also provides a facile approach to constructing high-performance multifunctional luminescent materials, particularly those with strong and long-wavelength NIR absorption capabilities.
期刊：
Journal of Coordination Chemistry,2024年77(20-21):2363-2375 ISSN：0095-8972
通讯作者：
Zhang, Qian;Ou, YP
作者机构：
[Xia, Yonglin] Hengyang Normal Univ, Nanyue Coll, Dept Chem & Mat Sci, Hengyang 421008, Hunan, Peoples R China.;[Ou, Ya-Ping; Ou, YP; Gao, Chengshuo; Zhang, Qian; Liu, Zhengji] Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Organometall Mat Hunan Prov Coll, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Hunan, Peoples R China.
通讯机构：
[Ou, YP ; Zhang, Q] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Organometall Mat Hunan Prov Coll, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Hunan, Peoples R China.
关键词：
Benzo[1,2-b:4,5-b']dithiophene;Ruthenium ethynyl complexes;Spectroelectrochemistry;Charge delocalization;Redox process
摘要：
We have constructed isomeric triruthenium ethynyl complexes 1 and 2 linked by benzo[1,2-b:4,5-b']dithiophene. The electronic properties of 1 and 2 were compared by (spectro)electrochemical and theoretical calculations. DFT (density functional theory) fully-optimized structures 1 and 2 showed that the ruthenium terminal groups both exhibit a similar pseudo-octahedral configuration as reported for the crystal structure of 1. With step-by-step oxidation, the bond length of Ru-C decreases and the bond length of C equivalent to C increases, which indicated that the complexes undergo a transition from Ru-C equivalent to C to Ru = C = C. The electrochemical results of 1 and 2 featured two consecutive single-electron redox processes, and the Delta E value of 2 (329 mV) was significantly higher than that of 1 (140 mV). The near-IR broad absorptions of 2(+) from UV-Vis-NIR spectroelectrochemistry exhibited a blue shift relative to that of 1(+), which could be attributed to MLCT (metal to ligand charge transfer) absorptions and confirmed by TDDFT (time dependent) calculations. The results suggested that the bridge ligands are involved in the redox process. The nu(C equivalent to C) stretch of 2(+) from IR spectroelectrochemistry exhibited a strong single peak at 1969 cm(-1), while the isomer 1(+) showed three asymmetric peaks. These results showed excellent charge delocalization ability of 2.
摘要：
Developing novel photoelectric functional materials based on dithienylethenes (DTEs) building block has drawn increasing attention due to their excellent photochromic properties. In this contribution, two D-A type DTE derivatives 3 and 4 bearing triphenylamine (TPA) and anthraquinone (or anthracene) groups have been synthesized, and their structures have been characterized by means of NMR and MS. The UV–vis spectroscopy results show that compounds 3 and 4 exhibited reversible photochromism in toluene and THF solutions under UV/vis light irradiation , featuring good fatigue resistance and responsiveness. However, almost no photochromic properties for DTEs 3 and 4 were observed in larger polar DMSO . Interestingly, DTE 3 with obvious push-pull characteristics also displayed visible-light driven photochromic behavior in toluene. Meanwhile, fluorescence spectroscopy experiments have shown that DTE 4 with the anthracene fluorescent group showed fluorescent switching properties upon UV/vis light irradiation in toluene and THF solutions. The electrochemical results revealed a certain decrease in the half-wave potential of TPA-based 3 and 4 after UV irradiation , suggesting that the increasing conjugation degree of the ring-closed isomers results in the increase of HOMO orbital energy and the decrease of HOMO-LUMO gap and is beneficial for the occurrence of oxidation process , which are further proved by DFT calculations. TDDFT predicts that the transition absorption of the ring-closed isomers 3c and 4c respectively at 615 nm and 651 nm mainly come from π-π* mixed with TPA→anthraquinone CT or TPA→anthracene CT transition, which is consistent with the experimental results.
Developing novel photoelectric functional materials based on dithienylethenes (DTEs) building block has drawn increasing attention due to their excellent photochromic properties. In this contribution, two D-A type DTE derivatives 3 and 4 bearing triphenylamine (TPA) and anthraquinone (or anthracene) groups have been synthesized, and their structures have been characterized by means of NMR and MS. The UV–vis spectroscopy results show that compounds 3 and 4 exhibited reversible photochromism in toluene and THF solutions under UV/vis light irradiation , featuring good fatigue resistance and responsiveness. However, almost no photochromic properties for DTEs 3 and 4 were observed in larger polar DMSO . Interestingly, DTE 3 with obvious push-pull characteristics also displayed visible-light driven photochromic behavior in toluene. Meanwhile, fluorescence spectroscopy experiments have shown that DTE 4 with the anthracene fluorescent group showed fluorescent switching properties upon UV/vis light irradiation in toluene and THF solutions. The electrochemical results revealed a certain decrease in the half-wave potential of TPA-based 3 and 4 after UV irradiation , suggesting that the increasing conjugation degree of the ring-closed isomers results in the increase of HOMO orbital energy and the decrease of HOMO-LUMO gap and is beneficial for the occurrence of oxidation process , which are further proved by DFT calculations. TDDFT predicts that the transition absorption of the ring-closed isomers 3c and 4c respectively at 615 nm and 651 nm mainly come from π-π* mixed with TPA→anthraquinone CT or TPA→anthracene CT transition, which is consistent with the experimental results.
摘要：
著名学者 Benedict Richard Anderson 曾说:"民族是一种想象的共同体."1民族共同体的建立依托于与本民族有关的诸多因素,它们在历史发展的过程中建立起盘根错节的联系,同时以一种特殊的想象力链接在一起,构成不可分割的整体.湘西地区民族构成多样化,苗族、土家族、侗族、瑶族等都是在本地生活时间较长,历史悠久,民族文化深厚的原住少数民族,也逐渐形成了它们特有的意识基础与特色文化,本土民族民间音乐也很丰富.
期刊：
Results in Physics,2023年54:107047 ISSN：2211-3797
通讯作者：
Lan, Y;Huang, WQ
作者机构：
[Zhang, Jing; Luo, Jia-Cheng; He, Zi-Cheng] Hengyang Normal Univ, Nanyue Coll, Dept Phys & Elect Informat Sci, Hengyang 421008, Peoples R China.;[Lan, Yu] Hengyang Normal Univ, Coll Phys & Elect Engn, Hengyang 421002, Peoples R China.;[Huang, Wei-Qing; Huang, Gui-Fang] Hunan Univ, Sch Phys & Elect, Dept Appl Phys, Changsha 410082, Peoples R China.;[Hu, Wangyu] Hunan Univ, Sch Mat Sci & Engn, Changsha 410082, Peoples R China.
通讯机构：
[Lan, Y ; Huang, WQ ] H;Hengyang Normal Univ, Coll Phys & Elect Engn, Hengyang 421002, Peoples R China.;Hunan Univ, Sch Phys & Elect, Dept Appl Phys, Changsha 410082, Peoples R China.
关键词：
Schottky barrier;Metal-semiconductor contact;van der Waals heterostructure;Electric field;First -principles calculations
摘要：
Two-dimensional (2D) transition metal carbides, nitrides, or carbonitrides (MXenes) have emerged as promising ultrathin materials for nanoelectronics and optoelectronics. However, the contact barrier at metal–semiconductor (MS) junctions still significantly limits the device's performance. Here, we propose a novel strategy—functionalizing accompanied with external electric fields—to tune the MS contact nature in MXene-based van der Waals (vdW) heterostructures, taking 2D Ti 2 C as an example, by means of first-principles calculations. Different Ti 2 CO 2 /Ti 2 CX 2 (X = OH or S) vdW heterostructures are designed via functionalizing Ti 2 C metals to contact with 2D Ti 2 CO 2 . We reveal that OH functionalized vdW MS heterostructure (Ti 2 CO 2 /Ti 2 C(OH) 2 ) can be tuned to the Ohmic contact owing to the strong interlayer interaction inducing a large number of interlayer transferred electrons; while for the sulfurized vdW MS heterostructure (Ti 2 CO 2 /Ti 2 CS 2 ), its Schottky barrier height and contact type can be effectively tuned by external electric field due to the rather weak interlayer interaction. Our work paves a new way for the construction of 2D MXene-based vdW MS heterostructures and demonstrates the great potential of 2D MXenes in future nanoelectronics and optoelectronics.
Two-dimensional (2D) transition metal carbides, nitrides, or carbonitrides (MXenes) have emerged as promising ultrathin materials for nanoelectronics and optoelectronics. However, the contact barrier at metal–semiconductor (MS) junctions still significantly limits the device's performance. Here, we propose a novel strategy—functionalizing accompanied with external electric fields—to tune the MS contact nature in MXene-based van der Waals (vdW) heterostructures, taking 2D Ti 2 C as an example, by means of first-principles calculations. Different Ti 2 CO 2 /Ti 2 CX 2 (X = OH or S) vdW heterostructures are designed via functionalizing Ti 2 C metals to contact with 2D Ti 2 CO 2 . We reveal that OH functionalized vdW MS heterostructure (Ti 2 CO 2 /Ti 2 C(OH) 2 ) can be tuned to the Ohmic contact owing to the strong interlayer interaction inducing a large number of interlayer transferred electrons; while for the sulfurized vdW MS heterostructure (Ti 2 CO 2 /Ti 2 CS 2 ), its Schottky barrier height and contact type can be effectively tuned by external electric field due to the rather weak interlayer interaction. Our work paves a new way for the construction of 2D MXene-based vdW MS heterostructures and demonstrates the great potential of 2D MXenes in future nanoelectronics and optoelectronics.
