Citation: Shao-Zhuang ZHANG, Chi-Xiao MA, Hai-Yang GUO, Jian-Hui SHE, Jun-Yong ZHANG, Yan-Bo SHI, Guo-Dong LI, Xiao-Ming REN, Jing-Li XIE. Preparation and Characterization of Copper Complexes of Schiff Base Ligands Synthesized In Situ from Spiropyran Derivative[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(2): 353-360. doi: 10.11862/CJIC.2022.032 shu

Preparation and Characterization of Copper Complexes of Schiff Base Ligands Synthesized In Situ from Spiropyran Derivative

Shao-Zhuang ZHANG ^{1, 2} ,
Chi-Xiao MA ² ,
Hai-Yang GUO ² ,
Jian-Hui SHE ² ,
Jun-Yong ZHANG ^2,, ,
Yan-Bo SHI ^3,, ,
Guo-Dong LI ⁴ ,
Xiao-Ming REN ^1,, ,
Jing-Li XIE ^{2, 4,,}

1.
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China
2.
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, Zhejiang 314001, China
3.
Central Laboratory of Jiaxing Traditional Chinese Medicine Hospital, Jiaxing Key Laboratory of Diabetic Angiopathy Research, Jiaxing, Zhejiang 314000, China
4.
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China

Corresponding author: Jun-Yong ZHANG, zhangjy@mail.zjxu.edu.cn Yan-Bo SHI, shiyanbocas@163.com Xiao-Ming REN, xmren@njtech.edu.cn Jing-Li XIE, jlxie@mail.zjxu.edu.cn
Received Date: 15 January 2021
Revised Date: 8 November 2021

Figures(8)

By virtue of Schiff base ligands bis(2-(methyliminomethyl)-4-nitro-phenol) dianion (L₁)/2-((3-aminopropylimino)-methyl)-4-nitro-phenol monoanion (L₂) that derived from photochromic molecule 2-(3', 3'-dimethyl-6-nitrospiro(chromene-2, 2'-indolin)-1'-yl)ethanol, two metal-organic complexes[Cu(L₁)] (1) and[Cu(L₂)(1, 3-DAP)]NO₃ (2) have been successfully fabricated through in situ ligand reaction in the presence of Cu²⁺. These complexes were characterized by IR, single-crystal X-ray diffraction, and powder X-ray diffraction. Additionally, certain photocatalytic properties of the two complexes for the degradation of organic dye molecules have been observed.
- Schiff base ligand,
- in situ reaction,
- spiropyran,
- photocatalytic activity
1. [1]
  Al-Sahlanee T Q M, Al-Amery M H. Synthesis, Characterization, Antioxident and Anticancer Human Studies of New Metal Ion Complexes of Poly Schiff Base Derived from 4-Aminocetophenone with Salicylaldehyde and 4-Bromoaniline[J]. Asian J. Pharm. Clin. Res., 2018,11:489-493.
2. [2]
  Zoubi W A, Al-Hamdani A A S, Kaseem M, Ahmed S D, Ko Y G. A New Azo-Schiff Base: Synthesis, Characterization, Biological Activity and Theoretical Studies of Its Complexes[J]. Appl. Organomet. Chem., 2016,30:810-817. doi: 10.1002/aoc.3506
3. [3]
  Malik M A, Dar O A, Gull P, Wani M Y. Heterocyclic Schiff Base Transition Metal Complexes in Antimicrobial and Anticancer Chemotherapy[J]. MedChemComm, 2018,9:409-436. doi: 10.1039/C7MD00526A
4. [4]
  Gayen F R, Ali A A, Bora D, Roy S, Saha S, Saikia L, Goswamee R L, Saha B. Correction: A Ferrocene Functionalized Schiff Base Containing Cu(Ⅱ) Complex: Synthesis, Characterization and Parts-Per-Million Level Catalysis for Azide Alkyne Cycloaddition[J]. Dalton Trans., 2020,49:6578-6586. doi: 10.1039/D0DT00915F
5. [5]
  Xu Y J, Kaneko K, Kanai M, Shibasaki M, Matsunaga S. Regiodivergent Kinetic Resolution of Terminal and Internal rac-Aziridines with Malonates under Dinuclear Schiff Base Catalysis[J]. J. Am. Chem. Soc., 2014,136(25):9190-9194. doi: 10.1021/ja5039165
6. [6]
  Liu X, Hamon J R. Recent Developments in Penta-, Hexa- and Hepta-dentate Schiff Base Ligands and Their Metal Complexes[J]. Coord. Chem. Rev., 2019,389(15):94-118.
7. [7]
  Cozzi P G. Metal-Salen Schiff Base Complexes in Catalysis: Practical Aspects[J]. Chem. Soc. Rev., 2004,33(7):410-421. doi: 10.1039/B307853C
8. [8]
  Shellaiah M, Wu Y H, Singh A, Raju M V R, Lin H C. Novel Pyrene- and Anthracene-Based Schiff Base Derivatives as Cu²⁺ and Fe³⁺ Fluorescence Turn-On Sensors and for Aggregation Induced Emissions[J]. J. Mater. Chem. A, 2013,1:1310-1318. doi: 10.1039/C2TA00574C
9. [9]
  Berbasova T, Nosrati M, Vasileiou C, Wang W J, Lee K S S, Yapici I, Geiger J H, Borhan B. Rational Design of a Colorimetric pH Sensor from a Soluble Retinoic Acid Chaperone[J]. J. Am. Chem. Soc., 2013,135(43):16111-16119. doi: 10.1021/ja404900k
10. [10]
  El-Shishtawy R M, Al-Ghamdi H A, Alam M M, Al-Amshany Z M, Asiri A M, Rahman M M. Development of Cd²⁺ Sensor Based on BZNA/Nafion/Glassy Carbon Electrode by Electrochemical Approach[J]. Chem. Eng. J., 2018,352(15):225-231.
11. [11]
  Liu X, Fu C H, Ren X L, Liu H Y, Li L L, Meng X W. Fluorescence Switching Method for Cascade Detection of Salicylaldehyde and Zinc(Ⅱ) Ion Using Protein Protected Gold Nanoclusters[J]. Biosens. Bioelectron., 2015,74(15):322-328.
12. [12]
  Das M, Biswas A, Kundu B K, Charmier M A J, Mukherjee A, Mobin S M, Udayabhanu G, Mukhopadhyay S. Enhanced Pseudo-Halide Promoted Corrosion Inhibition by Biologically Active Zinc(Ⅱ) Schiff Base Complexes[J]. Chem. Eng. J., 2019,357(1):447-457.
13. [13]
  Bedair M A, El-Sabbah M M B, Fouda A S, Elaryian H M. Synthesis, Electrochemical and Quantum Chemical Studies of Some Prepared Surfactants Based on Azodye and Schiff Base as Corrosion Inhibitors for Steel in Acid Medium[J]. Corros. Sci., 2017,128:54-72. doi: 10.1016/j.corsci.2017.09.016
14. [14]
  Saha S Kr, Banerjee P. Introduction of Newly Synthesized Schiff Base Molecules as Efficient Corrosion Inhibitors for Mild Steel in 1 M HCl Medium: An Experimental, Density Functional Theory and Molecular Dynamics Simulation Study[J]. Mater. Chem. Front., 2018,2:1674-1691. doi: 10.1039/C8QM00162F
15. [15]
  Sun H, Sun S S, Han F F, Ni Z H, Zhang R, Li M D. A New Tetraphenylethene-Based Schiff Base: Two Crystalline Polymorphs Exhibiting Totally Different Photochromic and Fluorescence Properties[J]. J. Mater. Chem. C, 2019,7:7053-7060.
16. [16]
  Guo S L, Liu G, Fan C B, Pu S Z. A New Diarylethene-Derived Probe for Colorimetric Sensing of Cu(Ⅱ) and Fluorometric Sensing of Cu(Ⅱ) and Zn(Ⅱ): Photochromism and High Selectivity[J]. Sens. Actuators B, 2018,266(1):603-613.
17. [17]
  Pu S Z, Tong Z P, Liu G, Wang R J. Multi-Addressable Molecular Switches Based on a New Diarylethene Salicylal Schiff Base Derivative[J]. J. Mater. Chem. C, 2013,1:4726-4739. doi: 10.1039/c3tc30804a
18. [18]
  Mukhopadhyay A, Maka V K, Moorthy J N. Fluoride-Triggered Ring-Opening of Photochromic Diarylpyrans into Merocyanine Dyes: Naked-Eye Sensing in Subppm Levels[J]. J. Org. Chem., 2016,81(17):7741-7750. doi: 10.1021/acs.joc.6b01361
19. [19]
  Zhang J J, Fu Y X, Han H H, Zang Y, Li J, He X P, Feringa B L, Tian H. Remote Light-Controlled Intracellular Target Recognition by Photochromic Fluorescent Glycoprobes[J]. Nat. Commun., 2017,8987. doi: 10.1038/s41467-017-01137-8
20. [20]
  Lin S Y, Gutierrez-Cuevas K G, Zhang X F, Guo J B, Li Q. Fluorescent Photochromic Alpha-Cyanodiarylethene Molecular Switches: An Emerging and Promising Class of Functional Diarylethene[J]. Adv. Funct. Mater., 20202007957.
21. [21]
  Ali A A, Kharbash R, Kim Y. Chemo- and Biosensing Applications of Spiropyran and Its Derivatives: A Review[J]. Anal. Chim. Acta, 2020,1110(8):199-223.
22. [22]
  Zacharias P, Gather M C, Kohnen A, Rehmann N, Meerholz K. Photoprogrammable Organic Light-Emitting Diodes[J]. Angew. Chem. Int. Ed., 2009,48:4038-4041. doi: 10.1002/anie.200805969
23. [23]
  Feuerstein T J, Muller R, Barner-Kowollik C, Roesky P W. Investigating the Photochemistry of Spiropyran Metal Complexes with Online LED-NMR[J]. Inorg. Chem., 2019,58(22):15479-15486. doi: 10.1021/acs.inorgchem.9b02547
24. [24]
  Wales D J, Cao Q, Kastner K, Karjalainen E, Newton G N, Sans V. 3D-Printable Photochromic Molecular Materials for Reversible Information Storage[J]. Adv. Mater., 2018,30(26)1870193. doi: 10.1002/adma.201870193
25. [25]
  Tian H. Data Processing on a Unimolecular Platform[J]. Angew. Chem. Int. Ed., 2010,49(28):4710-4712. doi: 10.1002/anie.200906834
26. [26]
  Raymo F M, Alvarado R J, Giordani S, Cejas M A. Memory Effects Based on Intermolecular Photoinduced Proton Transfer[J]. J. Am. Chem. Soc., 2003,125(8):2361-2364. doi: 10.1021/ja027977j
27. [27]
  Miguez F B, Menzonatto T G, Netto J F Z, Silva I M S, Verano-Braga T, Lopes J F, DeSousa F B. Photo-Dynamic and Fluorescent Zinc Complex Based on Spiropyran Ligand[J]. J. Mol. Struct., 2020,1211(5)128105.
28. [28]
  Funasako Y, Miyazaki H, Sasaki T, Goshima K, Inokuchi M. Synthesis, Photochromic Properties, and Crystal Structures of Salts Containing a Pyridinium-Fused Spiropyran: Positive and Negative Photochromism in the Solution and Solid State[J]. J. Phys. Chem. B, 2020,124(33):7251-7257. doi: 10.1021/acs.jpcb.0c04994
29. [29]
  Qu L, Xu X M, Song J T, Wu D H, Wang L, Zhou W L, Zhou X G, Xiang H F. Solid-State Photochromic Molecular Switches Based on Axially Chiral and Helical Spiropyrans[J]. Dyes Pigm., 2020,181108597. doi: 10.1016/j.dyepig.2020.108597
30. [30]
  Cui H Q, Liu H, Chen S, Wang R M. Synthesis of Amphiphilic Spiropyran-Based Random Copolymer by Atom Transfer Radical Polymerization for Co²⁺ Recognition[J]. Dyes Pigm., 2015,115:50-57. doi: 10.1016/j.dyepig.2014.12.008
31. [31]
  Hu S Z, Lv L H, Chen S H, You M L, Fu Z Y. Zn-MOF-Based Photoswitchable Dyad that Exhibits Photocontrolled Luminescence[J]. Cryst. Growth Des., 2016,16(12):6705-6708. doi: 10.1021/acs.cgd.6b01129
32. [32]
  Zhang H, Kou X X, Zhang Q, Qu D H, Tian H. Altering Intercomponent Interactions in a Photochromic Multi-State Rotaxane[J]. Org. Biomol. Chem., 2011,9:4051-4056. doi: 10.1039/c1ob05307h
33. [33]
  Poelma S O, Oh S S, Helmy S, Knight A S, Burnett G L, Soh H T, Hawker C, Dealaniz J R. Controlled Drug Release to Cancer Cells from Modular One-Photon Visible Light-Responsive Micellar System[J]. Chem. Commun., 2016,52:10525-10528. doi: 10.1039/C6CC04127B
34. [34]
  Guo X, Shao B H, Zhou S B, Aprahamian I, Chen Z. Visualizing Intracellular Particles and Precise Control of Drug Release Using an Emissive Hydrazone Photochrome[J]. Chem. Sci., 2020,11:3016-3021. doi: 10.1039/C9SC05321B
35. [35]
  Cardano F, Delcanto E, Giordani S. Spiropyrans for Light-Controlled Drug Delivery[J]. Dalton Trans., 2019,48:15537-15544. doi: 10.1039/C9DT02092F
36. [36]
  Tong R, Hemmati H D, Langer R, Kohane D S. Photoswitchable Nanoparticles for Triggered Tissue Penetration and Drug Delivery[J]. J. Am. Chem. Soc., 2012,134(21):8848-8855. doi: 10.1021/ja211888a
37. [37]
  Achilleos D S, Hatton T A, Vamvakaki M. Light-Regulated Supramolecular Engineering of Polymeric Nanocapsules[J]. J. Am. Chem. Soc., 2012,134(13):5726-5729. doi: 10.1021/ja212177q
38. [38]
  Ye Z W, Yu H B, Yang W, Zheng Y, Li N, Bian H, Wang Z C, Liu Q, Song Y T, Zhang M Y, Xiao Y. Strategy to Lengthen the On-Time of Photochromic Rhodamine Spirolactam for Super-resolution Photoactivated Localization Microscopy[J]. J. Am. Chem. Soc., 2019,141(16):6527-6536. doi: 10.1021/jacs.8b11369
39. [39]
  Deniz E, Tomasulo M, Cusido J, Yildiz I, Petriella M, Bossi M L, Sortino S, Raymo F M. Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes[J]. J. Phys. Chem. C, 2012,116(10):6058-6068.
40. [40]
  Xie J L, Batten S R, Zou Y, Ren X M. Observation of In Situ Ligand Reactions during the Assembly of Crystalline Zn-S Clusters[J]. Cryst. Growth Des., 2011,11:16-20. doi: 10.1021/cg100926g
41. [41]
  Liu W L, Yu J H, Jiang J H, Yuan L M, Xu B, Liu Q A, Qu B T, Zhang G Q, Yan C G. Hydrothermal Syntheses, Structures and Luminescent Properties of Zn Coordination Polymers Assembled with Benzene-1, 2, 3-tricarboxylic Acid Involving In Situ Ligand Reactions[J]. CrystEngComm, 2011,13:2764-2773.
42. [42]
  Hou Y L, PengY L, Diao Y X, Liu J, Chen L Z, Li D. Side Chain Induced Self-Assembly and Selective Catalytic Oxidation Activity of Copper-Copper-N-4 Complexes[J]. Cryst. Growth Des., 2020,20:1237-1241.
43. [43]
  Wei R P, Dong Y T, Zhang Y Y, Zhang R, Al-Tahan M A, Zhang J M. In-Situ Self-Assembled Hollow Urchins F-Co-MOF on rGO as Advanced Anodes for Lithium-Ion and Sodium-Ion Batteries[J]. J. Colloid Interface Sci., 2021,582:236-245.
44. [44]
  Zhang W Q, Kang Y F, Guo L L, Yang J J. Synthesis, Structure and Fluorescent Property of a Novel 3D Rod-Packing Microporous Zn(Ⅱ) MOF Based on a Temperature-Induced In Situ Ligand Reaction[J]. ChemistrySelect, 2020,5:1439-1442.
45. [45]
  Dunning S G, Reynolds J E, Walsh K M, Kristek D J, Lynch V M, Kunal P, Humphrey S M. Direct, One-Pot Syntheses of MOFs Decorated with Low-Valent Metal-Phosphine Complexes[J]. Organometallics, 2019,38:3406-3411.
46. [46]
  Baldrighi M, Locatelli G, Desper J, Aakeroy C B, Giordani S. Probing Metal Ion Complexation of Ligands with Multiple Metal Binding Sites: The Case of Spiropyrans[J]. Chem. Eur. J., 2016,22(39):13976-13984.
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