Citation: Ting-Ying YANG, Dan GUO, Yu-Qiong HU, Si-Jia YI, Shu-Qi GU, Xia HE, Xiao-Ming ZHU, Fu-Xing ZHANG. Synthesis, structure, and properties of multinuclear Ca(Ⅱ) and binuclear Mn(Ⅱ) complexes assembled by 1, 10-phenanthroline and 1-naphthalic acid ligands[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(1): 117-126. doi: 10.11862/CJIC.2022.282 shu

Synthesis, structure, and properties of multinuclear Ca(Ⅱ) and binuclear Mn(Ⅱ) complexes assembled by 1, 10-phenanthroline and 1-naphthalic acid ligands

Hunan Engineering Research Center for Monitoring and Treatment of Heavy Metals Pollution in the Upper Reaches of Xiangjiang River, Key Laboratory of Functional Metal-Organic Compounds of Hunan Province, Key Laboratory of Organometallic New Materials, College of Hunan Province, College of Chemistry and Material Science, Hengyang Normal University, Hengyang, Hunan 421008, China

Corresponding author: Xiao-Ming ZHU, zxmhunhy@163.com Fu-Xing ZHANG, zfx8056@163.com
Received Date: 18 July 2022
Revised Date: 10 November 2022

Figures(7)

Two complexes [Ca(Phen)(Nap)₂]_n (1) and [Mn₂(Phen)₂(Nap)4(H₂O)] (2) were synthesized by calcium acetate monohydrate or manganous acetate reacting with 1, 10-phenanthroline (Phen) and 1-naphthoic acid (HNap). Complexes 1 and 2 have been characterized by IR, elemental analysis, and thermogravimetry and the crystal structures have been determined by X-ray diffraction. Both the central calcium ion and the central manganese ion form a six-coordinated twisted octahedral structure. The excitation spectrum and emission spectrum of the two complexes were determined, and the results showed that the excitation and emission spectra of the complexes had a good mirror relationship, and the Stokes shift of complex 2 was greater than that of complex 1. In vitro antitumor activities of both complexes were evaluated by MTT against three human cancer cell lines, namely human lung cancer cells (NCI-H460), human breast cancer cells (MCF-7), human liver cancer cells (HepG2), and human normal cells (HL7702). It was found that complexes 1 and 2 showed a good inhibitory effect on the three cancer cells, compared to the normal cell. The interactions of the complexes with calf thymus DNA have been studied by UV and fluorescence spectroscopy, and the results show that the binding mode of complexes 1 and 2 with DNA may most likely bind in the groove of the DNA backbone by electrostatic action, and their intrinsic binding constants were 5.83×10³ and 6.43×10³ L·mol^-1, respectively. Complex 1 showed no redshift, while complex 2 showed an obvious redshift of 2.0 nm. The subtractive effect, intrinsic binding constants, and the redshift data indicate that the interaction between complex 2 and DNA is greater than that between complex 1 and DNA.
- multinuclear Ca(Ⅱ) complex,
- binuclear Mn(Ⅱ) complex,
- crystal structure,
- DNA-binding,
- in vitro antitumor activity
1. [1]
  Jiang D N, Huang C, Zhu J, Wang P, Liu Z M, Fang D. Classification and role of modulators on crystal engineering of metal organic frameworks (MOFs)[J]. Coord. Chem. Rev., 2021,444214064. doi: 10.1016/j.ccr.2021.214064
2. [2]
  Panicker R R, Sivaramakrishna A. Remarkably flexible 2, 2': 6', 2″-terpyridines and their group 8-10 transition metal complexes-Chemistry and applications[J]. Coord. Chem. Rev., 2022,459214426. doi: 10.1016/j.ccr.2022.214426
3. [3]
  Reek J N H, Bruin B D, Pullen S, Mooibroek T J, Kluwer A M, Caumes X. Transition metal catalysis controlled by hydrogen bonding in the second coordination sphere[J]. Chem. Rev., 2022,122(14):12308-12369. doi: 10.1021/acs.chemrev.1c00862
4. [4]
  Zhang J P, Zhang Y B, Lin J B, Chen X M. Metal azolate frameworks: From crystal engineering to functional materials[J]. Chem. Rev., 2012,112:1001-1033. doi: 10.1021/cr200139g
5. [5]
  Liu W, Gust R. Metal N-heterocyclic carbene complexes as potential antitumor metallodrugs[J]. Chem. Soc. Rev., 2013,42(2):755-773. doi: 10.1039/C2CS35314H
6. [6]
  Rosenberg B, Vancamp L, Trosko J E, Mansour V H. Platinum compounds-A new class of potent antitumour agents[J]. Nature, 1969,222:385-386. doi: 10.1038/222385a0
7. [7]
  Sherman S E, Lippard S J. Structural aspects of platinum anticancer drug interactions with DNA[J]. Chem. Rev., 1987,87:1153-1181. doi: 10.1021/cr00081a013
8. [8]
  Marzilli L G, Ano S O, Intini F P, Natile G. New concepts relevant to cisplatin anticancer activity from unique spectral features providing evidence that adjacent guanines in d(GpG), intrastrand-cross-linked at N7 by a cis-platinum moiety, can adopt a head-to-tail arrangement[J]. J. Am. Chem. Soc., 1999,121:9133-9142. doi: 10.1021/ja9916409
9. [9]
  Howerton B S, Heidary D K, Glazer E C. Strained ruthenium complexes are potent light -activated anticancer agents[J]. J. Am. Chem. Soc., 2012,134(20):8324-8327. doi: 10.1021/ja3009677
10. [10]
  Devi J, Kumar B, Taxak B. Recent advancements of organotin(Ⅳ) complexes derived from hydrazone and thiosemicarbazone ligands as potential anticancer agents[J]. Inorg. Chem. Commun., 2022,139109208. doi: 10.1016/j.inoche.2022.109208
11. [11]
  LIU X, ZHANG F X, HE L F, LI D W, ZENG W H, JIANG S Y, HE X, SHENG L B, ZHU X M. Synthesis, structure and antitumor activity of two tris(o-bromobenzyl)tin carboxylates[J]. Chinese J. Inorg. Chem., 2022,38(1):46-52.
12. [12]
  Kaczmarek M T, Zabiszak M, Nowak M, Jastrzab R. Lanthanides: Schiff base complexes, applications in cancer diagnosis, therapy, and antibacterial activity[J]. Coord. Chem. Rev., 2018,370:42-54. doi: 10.1016/j.ccr.2018.05.012
13. [13]
  Hernández-Romero D, Rosete-Luna S, López-Monteon A, Chávez-Piña A, Pérez-Hernández N, Marroquín-Flores J, Cruz-Navarro A, Pesado-Gómez G, Morales-Morales D, Colorado-Peralta R. First-row transition metal compounds containing benzimidazole ligands: An overview of their anticancer and antitumor activity[J]. Coord. Chem. Rev., 2021,439213930. doi: 10.1016/j.ccr.2021.213930
14. [14]
  Nitiss J L. A copper connection to the uptake of platinum anticancer drugs[J]. Proc. Natl. Acad. Sci. U. S. A., 2002,99(22):13963-13965. doi: 10.1073/pnas.232574299
15. [15]
  Klein A V, Hambley T W. Platinum drug distribution in cancer cells and tumors[J]. Chem. Rev., 2009,109:4911-4920. doi: 10.1021/cr9001066
16. [16]
  Burger A M, Double J A, Newell D R. Inhibition of telomerase activity by cisplatin in human testicular cancer cells[J]. Eur. J. Cancer, 1997,33(4):638-644. doi: 10.1016/S0959-8049(96)00521-7
17. [17]
  HUANG C X, GU J, XIONG W M, CHEN J Z, NIE X L, SHANGGUAN X C. Synthesis, crystal structures and antibacterial activities of two complexes of Zn(Ⅱ)/Cd(Ⅱ) assembled by 4-carboxy-methoxycinnamic acid ligand[J]. Chinese J. Inorg. Chem., 2021,37(7):1197-1203.
18. [18]
  XU Y Z, SHEN J B, ZHAO G L, HU W J. Syntheses, crystal structures and DNA-binding of two manganese complexes[J]. Chinese J. Inorg. Chem., 2022,38(2):285-294.
19. [19]
  ZHU X M, FENG Y L, ZHANG F X, YU J X, JIANG W J, OU Y P, KUANG D Z. Synthesis, crystal structure and properties of dinuclear copper complex {[Cu(Phen)(Nap) ₂]₂·(EtOH)₂·(H₂O)} (Phen=1, 10-phenanthroline; Nap=1-naphthoic acid; EtOH=ethyl alcohol)[J]. Chinese Journal of Applied Chemistry, 2016,33(8):932-938.
20. [20]
  ZHANG C L, WANG J, LI J Y, YU X K, YANG J Y, CAI J H, LI Y Z, WANG H Y, GONG R Q. Synthesis of 1, 2, 4-triazine-phenanthroline Co(Ⅲ) complexes and their fluorescence recognition on calf thymus DNA[J]. Chinese Journal of Applied Chemistry, 2019,36(2):212-222.
21. [21]
  LIU Y C, CHEN Z F, LIANG H. Progress in research on pharmacological activities of calcium(Ⅱ) complexes of biorelevant ligands[J]. Progress in Pharmaceutical Sciences, 2020,44(4):269-279.
22. [22]
  Smith M R, Fernandes J, Go Y M, Jones D P. Redox dynamics of manganese as a mitochondrial life -death switch[J]. Biochem. Biophys. Res. Commun., 2017,482:388-398.
23. [23]
  Gunter T E, Gerstner B, Lester T, Wojtovich A P, Malecki J, Swarts S G, Brookes P S, Gavin C E, Gunter K K. An analysis of the effects of Mn²⁺ on oxidative phosphorylation in the liver, brain, and heart mitochondria using state 3 oxidation rate assays[J]. Toxicol. Appl. Pharmacol., 2010,249:65-75.
24. [24]
  WENG S F. Fourier transform infrared spectroscopy analysis. 2nd ed. Beijing: Chemical Industry Press, 2005: 305-306
25. [25]
  YANG S P, HAN L J, PAN Y, WU Z Y, HE X R, CHEN L J. Synthesis, crystal structure and antibacterial activity of a bismuth(Ⅲ) complex[Bi₂(PPA)₆·(Phen)₂] with phenylacetic acid and 1, 10-phenanthroline[J]. Acta Chim. Sinica, 2012,70(4):519-524.
26. [26]
  Lavis L D, Raines R T. Bright building blocks for chemical biology[J]. ACS Chem. Biol., 2014,9(4):855-866.
27. [27]
  Ren T B, Wang X, Zhang W, Zhang X X, Wang Z Y, Xiang Z, Yuan L, Zhang X B. A general method to increase Stokes shift by introducing alternating vibronic structures[J]. J. Am. Chem. Soc., 2018,140:7716-7722.
28. [28]
  LIU Y M, LI G Z, ZHANG H, LI Y J. Study on the fluorescence of ligustrazine hydrochloride and its application[J]. Chinese Journal of Spectroscopy Laboratory, 2001,18(4):536-538.
29. [29]
  CHEN L, DENG X, TAN Y X, ZHANG F X, KUANG D Z, JIANG W J. Synthesis, anti-tumor activity, and interaction with DNA of two substituted benzyltin complexes[J]. Chinese J. Inorg. Chem., 2022,38(6):1081-1089.
30. [30]
  XU J G, WANG Z B. Fluorescence analysis. 3rd ed. Beijing: Science Press, 2006: 64-70
31. [31]
  JIANG W J, TAN Y X, YU J X, ZHU X M, ZHANG F X, KUANG D Z. Syntheses, crystal structures and biological activity of 2-oxo-3-phenylpropionic acid aroyl hydrazone di-2, 4-dichlorobenzyltin complexes[J]. Chinese J. Inorg. Chem., 2016,32(8):1383-1390.
32. [32]
  DU F Y, LIN Q Y, QI Q Y, WEI Q, YANG L F, LIN Y P. Synthesis, structures and biological activity of transition-metal complexes with 2-substituted (The original is substitued) imidazole and demethyleantharic acid[J]. Sci. China-Chem., 2015,45(10):1050-1064.
33. [33]
  Bielawski K, Wolczynski S, Bielawska A. DNA-binding activity and cytotoxicity of the extended diphenylfuran bisamidines in breast cancer MCF-7 Cells[J]. Biol. Pharm. Bull., 2001,24(6):704-706.
34. [34]
  BAO F F, XU X X, ZHOU W, PANG C Y, XI S F, GU Z G, LI Z J. Synthesis, structures and DNA -binding of enantiomers of Fe(Ⅱ) and Ni(Ⅱ) Schiff base complexes[J]. Chinese J. Inorg. Chem., 2014,30(8):1748-1756.
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