Citation: Li-Xia FENG, Qiao-Ling LIU, Si-Si FENG, Yu-Cui HOU, Yue-Kui WANG. Chiroptical Properties of Mixed-Ligand Ruthenabenzene Complex[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(4): 665-674. doi: 10.11862/CJIC.2022.079 shu

Chiroptical Properties of Mixed-Ligand Ruthenabenzene Complex

1.
Department of Chemistry, Taiyuan Normal University, Jinzhong, Shanxi 030619, China
2.
Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China

Corresponding author: Li-Xia FENG, lxfeng@tynu.edu.cn Yue-Kui WANG, ykwang@sxu.edu.cn
Received Date: 7 November 2021
Revised Date: 18 February 2022

Figures(6)

The theoretical study of reaction mechanism and relationship between chiral configuration and property of chiral ruthenium complexes is an important topic. In this work, the chiroptical properties of the mixed-ligand ruthenabenzene complex [RuBen(PPh₃)₂(Phen) (L-Cys)]2+ (Phen=phenanthroline, L-Cys=L-cysteine) have been explored using the hybrid density functional theory (DFT). The geometrical and electronic structures and subsequent frequency verifications were calculated using the B3LYP method with the mixed basis set: the ECP28MWB pseudopotential with its (8s 7p6d2f)/[6s5p3d2f] valence basis set for ruthenium, and 6-311G(d) for other atoms. Based on these, the excited energies, rotational and oscillator strengths, as well as the electronic circular dichroism (ECD) spectra, were then calculated employing the time-dependent DFT method with the same functional and basis set. In all cases, solvent (water) effects were included using the polarized continuum model (PCM). Additionally, the intricate exciton-splitting pattern in the short wavelength region was analyzed using the exciton chirality method (ECM). The calculated ECD spectra were in good agreement with the observed ones as far as their band shape, signs, and relative intensities were concerned. The Λ/Δ configurations at the octahedral core dominate the distribution of the ECD curves, and the λ/δ twists of the L-Cys rings only affect the relative intensities of the absorption bands, while the contributions of the R/S chiral carbon atoms are negligible. The absorption bands above 340 nm are characterized by the π → π * transitions mixed with some metal-centered d → d transitions. The two pairs of ECD bands below 340 nm with clearly different intensities could be assigned to the classical (the strong one) and nonclassical (the weak one) exciton coupling, respectively. Both show a positive exciton-splitting pattern for the Λ-configuration, which could be used as a criterion to determine the absolute configurations of similar complexes. Additionally, comparing with mixed-ligand inorganic ruthenium complexes reveals the similarities and differences in their chiroptical properties.
- ruthenabenzene complex,
- electronic circular dichroism spectrum,
- chiroptical properties,
- exciton chirality method,
- exciton coupling
1. [1]
  XU Z X, LI L F, BAI X L, XU S F. Enantiomeric Helical Frameworks with dia Net Based on Rigid Ligands from Spontaneous Resolution[J]. Chinese J. Inorg. Chem., 2021,37(7):1191-1196.
2. [2]
  CHENG L, YANG J H, ZHAI Q C, ZHANG Q S. A Chiral Ag(Ⅰ) Coordination Polymer Based on an α, α-L-Diaryl Prolinol-Pyridine Derivative: Circular Dichroism, SHG Response and Luminescent Property[J]. Chinese J. Inorg. Chem., 2020,36(2):361-367.
3. [3]
  Zhao X, Nguyen E T, Hong A N, Feng P Y, Bu X H. Chiral Isocamphoric Acid: Founding a Large Family of Homochiral Porous Materials[J]. Angew. Chem. Int. Ed., 2018,57(24):7101-7105. doi: 10.1002/anie.201802911
4. [4]
  Santos A R, Escudero D, González L, Orellana G. Unravelling the Quenching Mechanisms of a Luminescent Ru^Ⅱ Probe for Cu^Ⅱ[J]. Chem. Asian J., 2015,10(3):622-629. doi: 10.1002/asia.201403340
5. [5]
  Knoll J D, Turro C. Control and Utilization of Ruthenium and Rhodium Metal Complex Excited States for Photoactivated Cancer Therapy[J]. Coord. Chem. Rev., 2015,282-283:110-126. doi: 10.1016/j.ccr.2014.05.018
6. [6]
  Estalayo-Adrián S, Garnir K, Moucheron C. Perspectives of Ruthenium Polyazaaromatic Photo -oxidizing Complexes Photoreactive towards Tryptophan-Containing Peptides and Derivatives[J]. Chem. Commun., 2018,54:322-337. doi: 10.1039/C7CC06542F
7. [7]
  Padhi S K, Fukuda R, Ehara M, Tanaka K. Photoisomerization and Proton-Coupled Electron Transfer (PCET) Promoted Water Oxidation by Mononuclear Cyclometalated Ruthenium Catalysts[J]. Inorg. Chem., 2012,51(9):5386-5392. doi: 10.1021/ic3003542
8. [8]
  Feng L X, Wang Y K, Jia J. Triplet Ground-State-Bridged Photochemical Process: Understanding the Photoinduced Chiral Inversion at the Metal Center of[Ru(phen)₂(L-Ser)] + and Its Bipy Analogues[J]. Inorg. Chem., 2017,56(23):14467-14476. doi: 10.1021/acs.inorgchem.7b02030
9. [9]
  Feng L X, Wang Y K. A Key Factor Dominating the Competition between Photolysis and Photoracemization of [Ru(bipy)₃]²⁺ and [Ru(phen)₃]²⁺ Complexes[J]. Inorg. Chem., 2018,57(15):8994-9001. doi: 10.1021/acs.inorgchem.8b00975
10. [10]
  Salassa L, Borfecchia E, Ruiu T, Garino C, Gianolio D, Gobetto R, Sadler P J, Cammarata M, Wulff M, Lamberti C. Photo-induced Pyridine Substitution in cis-[Ru(bpy)₂(py)₂]Cl₂: A Snapshot by Time-Resolved X-ray Solution Scattering[J]. Inorg. Chem., 2010,49(23):11240-11248. doi: 10.1021/ic102021k
11. [11]
  Wang Y, Wang Y K, Wang J M, Liu Y, Yang Y T. Theoretical Analysis of the Individual Contributions of Chiral Arrays to the Chiroptical Properties of Tris -diamine Ruthenium Chelates[J]. J. Am. Chem. Soc., 2009,131(25):8839-8847. doi: 10.1021/ja9004738
12. [12]
  Zhu J, Jia G C, Lin Z Y. Understanding Nonplanarity in Metallabenzene Complexes[J]. Organometallics, 2007,26(8):1986-1995. doi: 10.1021/om0701367
13. [13]
  Lin R, Zhao J, Chen H Y, Zhang H, Xia H P. Interconversion of Metallabenzenes and Cyclic η²-Allene-Coordinated Complexes[J]. Chem. Asian J., 2012,7(8):1915-1924. doi: 10.1002/asia.201200231
14. [14]
  Wang T D, Li S H, Zhang H, Lin R, Han F F, Lin Y M, Wen T B, Xia H P. Annulation of Metallabenzenes: From Osmabenzene to Osmabenzothiazole to Osmabenzoxazole[J]. Angew. Chem. Int. Ed., 2009,48(35):6453-6456. doi: 10.1002/anie.200902738
15. [15]
  Iron M A, Lucassen A C B, Cohen H, van der Boom M E, Martin J M L. A Computational Foray into the Formation and Reactivity of Metallabenzenes[J]. J. Am. Chem. Soc., 2004,126(37):11699-11710. doi: 10.1021/ja047125e
16. [16]
  Yang J, Jones W M, Dixon J K, Allison N T. Detection of a Ruthena-benzene, Ruthenaphenoxide, and Ruthenaphenanthrene Oxide: The First Metalla Aromatics of a Second-Row Transition Metal[J]. J. Am. Chem. Soc., 1995,117(38):9776-9777. doi: 10.1021/ja00143a029
17. [17]
  Zhang H, Xia H P, He G M, Wen T B, Gong L, Jia G C. Synthesis and Characterization of Stable Ruthenabenzenes[J]. Angew. Chem. Int. Ed., 2006,45(18):2920-2923. doi: 10.1002/anie.200600055
18. [18]
  Lin R, Zhang H, Li S H, Wang J N, Xia H P. New Highly Stable Metallabenzenes via Nucleophilic Aromatic Substitution Reaction[J]. Chem. Eur. J., 2011,17(15):4223-4231. doi: 10.1002/chem.201003566
19. [19]
  Zhang H, Lin R, Li J H, Zhu J, Xia H P. Interconversion between Ruthenacyclohexadiene and Ruthenabenzene: A Combined Experimental and Theoretical Study[J]. Organometallics, 2014,33(19):5606-5609. doi: 10.1021/om500550a
20. [20]
  Lin R, Zhang H, Li S H, Chen L, Zhang W, Wen T B, Zhang H, Xia H. pH-Switchable Inversion of the Metal-Centered Chirality of Metallabenzenes: Opposite Stereodynamics in Reactions of Ruthena-benzene with L-and D-Cysteine[J]. Chem. Eur. J., 2011,17(8):2420-2427. doi: 10.1002/chem.201001867
21. [21]
  Andrae D, Häußermann U, Dolg M, Stoll H, Preuß H. Energy-Adjusted Ab Initio Pseudopotentials for the Second and Third Row Transition Elements[J]. Theor. Chim. Acta, 1990,77(2):123-141. doi: 10.1007/BF01114537
22. [22]
  Martin J M L, Sundermann A. Correlation Consistent Valence Basis Sets for Use with the Stuttgart-Dresden-Bonn Relativistic Effective Core Potentials: The Atoms Ga-Kr and In-Xe[J]. J. Chem. Phys., 2001,114(8):3408-3420. doi: 10.1063/1.1337864
23. [23]
  Kurapkat G, Krüger P, Wollmer A, Fleischhauer J, Kramer B, Zobel E, Koslowski A, Botterweck H, Woody R W. Calculations of the CD Spectrum of Bovine Pancreatic Ribonuclease[J]. Biopolymers, 1997,41(3):267-287. doi: 10.1002/(SICI)1097-0282(199703)41:3<267::AID-BIP3>3.0.CO;2-Q
24. [24]
  Berova N, Polavarapu P L, Nakanishi K, Woody R W. Comprehensive Chiroptical Spectroscopy: Instrumentation, Methodologies, and Theoretical Simulations. New Jersey: John Wiley & Sons, 2012: 525-540
25. [25]
  Zhang H, Feng L, Gong L, Wu L Q, He G M, Wen T B, Yang F Z, Xia H P. Synthesis and Characterization of Stable Ruthenabenzenes Starting from HC≡CCH(OH)C≡CH[J]. Organometallics, 2007,26(10):2705-2713. doi: 10.1021/om070195k
26. [26]
  Bosnich B. The Absolute Configurations of Bis-Bidentate Chelate Compounds. The Case of the cis-Bis(pyridine)bis(o-phenanthroline)-Ruthenium(Ⅱ) Ion[J]. Inorg. Chem., 1968,7(1):178-180. doi: 10.1021/ic50059a044
1. [1]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
2. [2]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
3. [3]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
4. [4]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
5. [5]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
6. [6]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
7. [7]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004
8. [8]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
9. [9]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
10. [10]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
11. [11]
  Wei Li , Ze Chang , Meihui Yu , Ying Zhang . Curriculum Ideological and Political Design of Piezoelectricity Measurement Experiments of Coordination Compounds. University Chemistry, 2024, 39(2): 77-82. doi: 10.3866/PKU.DXHX202308004
12. [12]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
13. [13]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139
14. [14]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
15. [15]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
16. [16]
  Caixia Lin , Zhaojiang Shi , Yi Yu , Jianfeng Yan , Keyin Ye , Yaofeng Yuan . Ideological and Political Design for the Electrochemical Synthesis of Benzoxathiazine Dioxide Experiment. University Chemistry, 2024, 39(2): 61-66. doi: 10.3866/PKU.DXHX202309005
17. [17]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
18. [18]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
19. [19]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
20. [20]
  Zhuoming Liang , Ming Chen , Zhiwen Zheng , Kai Chen . Multidimensional Studies on Ketone-Enol Tautomerism of 1,3-Diketones By ¹H NMR. University Chemistry, 2024, 39(7): 361-367. doi: 10.3866/PKU.DXHX202311029

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(611)
HTML views(72)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142