作者机构：
[Wang, Hongqing; Xiao, Qianxiang; Li, Na; Meng, Lingyuan; Yan, Zhe; Wang, Xiao-Feng; Cao, Meng; Tan, Chunhong] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Tan, Chunhong] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China.
通讯机构：
[Xiao, QX; Wang, XF ; Tan, CH] U;[Tan, CH ] C;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China.
摘要：
We report the controlled preparation of kinetically and thermodynamically luminescent multinuclear cuprous coordination complexes. On reaction of the bidentate P/N-ligand (2-(diphenylphosphino)pyridine, abbreviated as dppy) and copper(I) with a similar stoichiometry but in different concentration conditions at ambient temperature, hexagonal crystals of [Cu-2(mu-dppy)(3)Cl]PF6 center dot CH2Cl2 (1) or polyhedron crystals of [Cu-4(mu-dppy)(6)Cl](PF6)(3) (2) were formed as kinetic or thermodynamic products, respectively. Investigation of the structures, morphologies, theoretical calculation, and photophysical properties of the multinuclear cuprous coordination complexes demonstrates the formation of and differences between kinetically and thermodynamically stable conformations. Single-crystal X-ray structural analyses indicated that 1 features the head-to-head orientation dppy bridged dinuclear trefoil-like Cu-2-core with one terminal Cl-, and tetranuclear 2 can be regarded as a Cl- bridged dimer of 1 with two-third flipping head-to-tail dppy ligands. The density functional theory (DFT) calculations demonstrated that 2 had a lower frontier molecular orbital energy than 1, with an energy difference of 320.76 kJ/mol. Intriguingly, the controllable reversible transformation between 1 and 2 can be achieved under suitable conditions. By soaking the crystal in the mother liquor or alcohol, the kinetically stable 1 can slowly transform to the thermodynamically stable 2, or conversely, 2 can also quickly reconstruct to 1 when it is soaked in a chloride solution. Steadily changing morphologies, photoluminescence, as well as powder X-ray diffraction patterns were observed during the gradual transformation process. Based on structural analyses, a feasible transforming mechanism was proposed. The energetic and structural analyses of and the interconversion process between kinetically and thermodynamically stable multicuprous complexes here provide insights into the relations among the structures, morphologies, and properties of the metal-organic coordination materials at the molecular level. [GRAPHICS]
作者机构：
[Lan, Wenbo; Wang, Xiaofeng] Xiangnan Univ, Sch Publ Hlth, Chenzhou, Hunan, Peoples R China.;[Guo, Wenlu] Hengyang Water Investment Grp Co Ltd, Hengyang, Peoples R China.;[Nie, CM; Guo, Wenlu; Nie, Changming] Univ South China, Sch Chem & Chem Engn, Hengyang, Peoples R China.
通讯机构：
[Nie, CM ] U;[Wang, XF ] X;Xiangnan Univ, Sch Publ Hlth, Chenzhou, Hunan, Peoples R China.;Univ South China, Sch Chem & Chem Engn, Hengyang, Peoples R China.
关键词：
asymmetric uranyl-Salophen;catalytic activity;chlorophenol;Wiberg bond indices
摘要：
This study employs density functional theory to investigate whether asymmetric uranyl‐salophen catalyzes the activation of 2,4‐dichlorophenol, 2,4,6‐trichlorophenol, and pentachlorophenol through an analysis of alterations in bond lengths, Wiberg indices, IR and UV‐Vis spectra, and 13C NMR shifts. The findings reveal elongated bond lengths and increased electrophilicity, indicating partial disruption of the aromatic system and potential catalytic activation, thereby suggesting a possible application for the degradation of chlorophenols in water. ABSTRACT This study employs density functional theory to investigate whether asymmetric uranyl‐Salophen catalyzes the activation of 2,4‐dichlorophenol, 2,4,6‐trichlorophenol, and pentachlorophenol. Changes in various important parameters such as bond lengths, Wiberg bond indices, infrared vibrational absorption spectra, natural charge distributions, ultraviolet–visible absorption spectra, and 13C NMR chemical shifts of the aromatic rings of chlorophenols before and after forming complexes with asymmetric uranyl‐Salophen are analyzed. This means that asymmetric uranyl‐Salophen indeed activates 2,4‐dichlorophenol, 2,4, 6‐trichlorophenol, and pentachlorophenol, significantly lengthening the aromatic ring bonds of the three chlorophenols and increasing the electrophilicity of the carbon atoms in the aromatic ring. This suggests that the conjugated system of the aromatic ring is also partially disrupted, indicating that these three chlorophenols are indeed catalytically activated. Furthermore, this implies that this asymmetric uranyl‐Salophen may be used to degrade chlorophenols in water.
作者机构：
[Lan, Wenbo] School of Public Health, Xiangnan University, Chenzhou, 423000, China;[Meng, Yanbin] School of Basic Medicine, Xiangnan University, Chenzhou, 423000, China;[Kong, Xianghe] School of Chemistry and Chemical Engineering, University of South China, Hengyang, 421000, China;[Wang, Xiaofeng] School of Public Health, Xiangnan University, Chenzhou, 423000, China. wangxf20161123@126.com;[Nie, Changming] School of Chemistry and Chemical Engineering, University of South China, Hengyang, 421000, China. changmingnie@usc.edu.cn
摘要：
The presence of chlorophenols in water poses a significant threat to human health and the environment. In response to this issue, a study was undertaken to evaluate the catalytic capabilities of chlorinated Heme towards common chlorophenols present in water, such as 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol. The study employed the B3LYP method, a sophisticated computational technique within density functional theory, to investigate the molecular interactions and transformations involved. It scrutinized structural parameters, Wiberg Bond Indices, which offer insights into the strength and nature of chemical bonds, along with spectroscopic data including infrared vibrational spectra, ultraviolet-visible absorption spectra, and molecular fluorescence spectra. Furthermore, the research analyzed molecular binding energies and orbital energy levels before and after the formation of complexes between Heme and the targeted chlorophenols. The findings indicate that Heme displays a notable activation characteristic towards these chlorophenols. This suggests that Heme could act as an effective catalyst in the degradation of chlorophenols in water, presenting a novel approach to water purification. The theoretical insights derived from this study are invaluable, potentially guiding the development of more efficient catalytic systems for treating chlorophenol-contaminated water, thereby reducing the environmental and health risks associated with these hazardous compounds.
期刊：
Separation and Purification Technology,2023年318:123951 ISSN：1383-5866
通讯作者：
Xiao-Feng Wang
作者机构：
[Xiao, Qianxiang; Wang, Xiao-Feng] School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, PR China;[Liu, Xiaolu; Yang, Xinyi; Liu, Yanfang] College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, PR China;[Wu, Weijin; Wang, Shiyu] School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, PR China<&wdkj&>College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, PR China
通讯机构：
[Xiao-Feng Wang] S;School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, PR China
摘要：
It is already known that nuclear power can reduce the greenhouse gas emissions, while must clear its release of a few but hazardous nuclear wastes. Therefore, there is an urgent need to rational design adsorption materials in order to excellent eliminate the radioactive contaminations, including the most potentially problematic technetium-99 (99Tc). Herein, we present an easily synthetic approach to prepare a robust imidazolium-based cationic organic polymer (denoted as PMV3m-Cl) in a low-cost, through vinyl polymerization via a tri-imidazolium-charged monomer. Due to the synergetic effects of physical adsorption and ion exchange, PMV3m-Cl featured ultrafast 99TcO4− (as well as its nonradioactive surrogate ReO4−) adsorption kinetics, with the performance of 99 % removal within 1 min (at a relatively low solid-to-liquid ratio of 0.2 g/L). PMV3m-Cl also displayed high adsorption performance of ReO4− over a wide range of pH values, and remained up to 94 % removal rate after five cycles of adsorption/desorption. Even in extreme alkaline (3 M NaOH) solution, it can remain stable and rapidly remove ReO4−, to reach the adsorption equilibriums at 30 s with a recorded removal efficiency of 79 %. Furthermore, it is noting that PMV3m-Cl enables to decontaminated low concentration (∼10 ppm) ReO4− contaminated potable water to residue of 7% within 1 min. The fast kinetics, excellent selectivity, and high uptake capacity (739 mg/g for ReO4−) of PMV3m-Cl were attributed to that the framework is rich in positively charged imidazole segments exhibiting the strong electrostatic interactions and binding affinity with ReO4− and 99TcO4− ions. Results of this study suggest PMV3m-Cl is a promising adsorbent for the removal of ReO4− and 99TcO4−, and provide valuable reference significance to design an alkaline resistant nuclear associated environmental remediation material.
期刊：
Proceedings of SPIE - The International Society for Optical Engineering,2023年12781 ISSN：0277-786X
通讯作者：
Li, Qianru(287465276@qq.com)
作者机构：
[Liu, Qiao] College of Chemistry & Biology and Environmental Engineering, Xiangnan University, Chenzhou, China;[Li, Qianru; Wang, Xiaofeng] School of public health, Xiangnan University, Chenzhou, China;[Lan, Wenbo] College of Chemical Engineering, University of South China, Hengyang, China;[Jing, Shuting] Food Business Section Municipal Center for Food and Drug Control, Chenzhou, China
通讯机构：
[Zeng, F.] C;[Wang, X.] S;College of Chemical and Biological Engineering, Hunan, China;School of Chemistry and Chemical Engineering, Hunan, China
期刊：
Proceedings of SPIE - The International Society for Optical Engineering,2022年12306 ISSN：0277-786X
通讯作者：
Wang, Xiaofeng(wangxf20161123@126.com)
作者机构：
[Lan, Wenbo; Wang, Xiaofeng; He, Liping; Liu, Yu; Tan, Bin; Chen, Cuimei; He, Ying; Wang, Liying] School of Public Health, Xiangnan University, Hunan, Chenzhou;423000, China;[Meng, Yanbin] School of Basic Medical, Xiangnan University, Hunan, Chenzhou;School of Chemistry and Chemical Engineering, University of South China, 421000, China;Hengyang Water Investment Group Co. Ltd., Hunan, Hengyang
作者机构：
[Yanbin Meng] School of Basic Medicine, Xiangnan University, Chenzhou, China;[Jianhuang Li] Office of Network Information Technology, Xiangnan University, Chenzhou, China;[Xiaofeng Wang; Wenbo Lan; Liping He; Binbin Wang; Yuzhu Wang; Liping Wang; Zhijian Bu] School of Public Health, Xiangnan University, Chenzhou, China;[Changming Nie] School of Chemistry and Chemical Engineering, University of South China, Hengyang, China
会议名称：
2022 7th International Conference on Intelligent Computing and Signal Processing (ICSP)
会议时间：
15 April 2022
会议地点：
Xi'an, China
会议论文集名称：
2022 7th International Conference on Intelligent Computing and Signal Processing (ICSP)
摘要：
In order to explore why heme can be used for the determination of lead, the central iron atom (Fe) of heme was replaced with lead atom (Pb). The structural characteristics and spectral characteristics of the molecules before and after the substitution, as well as the binding ability of the heme ligand to the central atom and the stability of the formed complex were compared. The results show that complex-Pb has obvious infrared characteristic spectrum and obvious ultraviolet absorption peak. After Fe in heme is replaced by Pb, the formed complex pb can exist stably, and the binding capacity of heme ligand to Pb is greater than that of Fe atom, and the chemical stability of complex pb is also better than that of heme.
作者机构：
[Feng, Yi; Li, Na; Cheng, Lu; Cao, Meng; Wang, Xiao-Feng; Tan, Chunhong] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Hunan, Peoples R China.;[Tan, Chunhong] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China.;[Sun, Yunkai] Changzhou Inst Technol, Sch Chem & Mat Sci, Changzhou 213022, Jiangsu, Peoples R China.
通讯机构：
[Chunhong Tan; Yunkai Sun; Xiao-Feng Wang] S;School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, P. R. China<&wdkj&>School of Chemistry and Materials Science, Changzhou Institute of Technology, Changzhou, Jiangsu, P. R. China<&wdkj&>School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, P. R. China<&wdkj&>State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, P. R. China
摘要：
The reactions of [Cu(CH3CN)(4)]ClO4 and 2-(diphenylphosphino)pyridine (dppy) with different halogen reagents NH4X (X = Cl-, Br- and l(-)) and four luminescent di-copper(i) coordination compounds, namely [Cu-2(mu-dppy)(3)Cl]ClO4 center dot H2O (1a), [Cu-2(mu-dppy)(3)Br]ClO4 (2a), Cu-2(mu-Br)(2)(mu-dppy)(eta-dppy)(2) (2b) and [Cu-2(mu-l)(2)(mu-dppy)(eta-dppy)(2)] (3b), were isolated. Intriguingly, X-ray crystallographic studies reveal that there were two kinds of Cue-core structural configuration induced by the differently sized halogen anions. With Cl--acting as a co-ligand, 1a featured a trefoil-like Cu-2-core with three mu(2)-dppy in a head-to-head orientation bridging two Cu(I) and one terminal Cl- occupying one axial position. On replacing Cl- with l(-), 3b comprised a butterfly-like Cue-core, being bridged by two I- anions and one mu(2)-dppy along with two terminal dppy. When Br- was employed, both the above types of Cu-2-cores were obtained in 2a and 2b, respectively. All these four di-copper(I) compounds exhibit intense green photoluminescence with microsecond lifetimes.
作者机构：
[Fang, Wei-Hui; Zhang, Jian; Zhang, Xue-Zhen] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China.;[Wang, Xiao-Feng] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Hunan, Peoples R China.
通讯机构：
[Wei-Hui Fang; Jian Zhang] S;State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China
摘要：
Aluminum is an important component for luminescence. However, the fluorescent aluminum complex with unambiguous structural information is still limited. Herein, we report a series of fluorescence aluminum oxo clusters (AlOCs). By introducing an additional coordination site to the aromatic conjugation ligand, cluster nuclearity increment and fluorescence variation are observed. Al-8(OH)(2)(mu(4)-O)(2)(1-NA)(2)(OEt)(16) (AlOC-41, 1-NA = 1-naphthoic acid, OEt = ethanol) is made up of two tetrahedral subunits. By introducing an additional coordination site to the aromatic conjugation ligand, we isolate a high nuclearity compound Al-10(mu(3)-O)(2)(3-HNA)(2)(OEt) (22) (AlOC-47, 3-HNA = 3-hydroxy-2-naphthoic acid). Correspondingly, their luminescence performance is different (blue fluorescence in AlOC-41 and green in AlOC-47). Present herein is a platform to illustrate the relationship between synthesis, structure, and fluorescence properties.
通讯机构：
[Guangchuan Ou] C;College of Chemistry and Bioengineering, Hunan University of Science and Engineering, Yongzhou 425199, Hunan, China<&wdkj&>Author to whom correspondence should be addressed.
摘要：
Five host-guest trimesic-acid-based hydrogen-bonds framework compounds with different guests, namely [(TMA)(4)center dot(TMB)(3)] (1), [(TMA)(2)center dot(DMB)(1.5)] (2), [(TMA)(6)center dot(MP)] (3), [(TMA)center dot(EP)] (4) and [(TMA)center dot(PP)] (5) (TMA = trimesic acid, TMB = 1,3,5-trimethoxybenzene, DMB = 1,4-dimethoxybenzene, MP = 4-methoxyphenol, EP = 4-ethoxyphenol and PP = 4-propoxyphenol), were obtained through co-crystallization, and were characterized by elemental analysis, infrared spectroscopy analysis, and thermogravimetric analysis. The trimesic acid molecules comprise a hydrogen bonding six-membered cyclic host network that is found in a two-dimensional arrangement in compounds 1 and 2, and in a nine-fold interpenetrated three-dimensional structure in compound 3. In compounds 4 and 5, the trimesic acid and EP/PP molecules form a hydrogen-bonded six-membered cyclic network, resulting in a one-dimensional chain structure through O-H horizontal ellipsis O hydrogen bonds.
作者机构：
[Zhang, Xue-Zhen; Wang, Xiao-Feng] Univ South China, Sch Chem & Chem Engn, 28 Changsheng Xi Rd, Hengyang 421001, Hunan, Peoples R China.;[Fang, Wei-Hui; Zhang, Xue-Zhen] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China.
通讯机构：
[Wei-Hui Fang; Xiao-Feng Wang] S;State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China<&wdkj&>School of Chemistry and Chemical Engineering, University of South China, No. 28, Changsheng Xi Road, Hengyang, Hunan 421001, China
作者机构：
[李奔可; 陈茵芝; 李小兰; 王晨扬; 谢睿; 王小峰] School of Chemistry and Chemical Engineering, University of South China, Hengyang;421001, China;[黄国基] China Academy of Launch Vehicle Technology, Beijing;100076, China;[李奔可; 陈茵芝; 李小兰; 王晨扬; 谢睿; 王小峰] 421001, China
通讯机构：
School of Chemistry and Chemical Engineering, University of South China, Hengyang, China
