Citation: Jiajia Song, Wei Duan, Yun Chen, Xiangyang Liu. Versatile Inorganic Oligomer-based Photochromic Spiropyrane Gels[J]. Chinese Journal of Structural Chemistry, ;2022, 41(5): 220503. doi: 10.14102/j.cnki.0254-5861.2022-0061 shu

Versatile Inorganic Oligomer-based Photochromic Spiropyrane Gels

Jiajia Song ¹ ,
Wei Duan ¹ ,
Yun Chen ^1,, ,
Xiangyang Liu ^{2, 3,,}

1.
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
2.
College of Ocean and Earth Sciences, College of Materials, College of Physical Science and Technology, State Key Laboratory of Marine Environmental Science (MEL), Research Institute for Biomimetics and Soft Matter, Xiamen University, Xiamen 361005, China
3.
Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542, Singapore

Corresponding author: Yun Chen, ychen@hnu.edu.cn Xiangyang Liu, liuxy@xmu.edu.cn
Received Date: 18 March 2022
Accepted Date: 8 April 2022

Figures(17)

Here we report an example of a general strategy for the immobilization of various different photochromic spiropyran molecules on eco-friendly cheap nanomatrix. The spiropyrans are encapsulated in calcium salt oligomers-based gels by centrifugation, forming an inorganic oligomer-based gelatinous photoswitchable hybrid material. Ca²⁺ is also used to regulate the optical properties of spiropyrans through chelation. The oligomer-based gel can not only provide the space required for photoisomerization, but also reduce the interference of the surrounding environment on the photochromic properties. Moreover, a practical paper-based and colloidal flexible substrate platform is constructed for the removal and naked-eye detection of liquid and gaseous hydrazine at room temperature based on the reactivity of the formyl group on spiropyrans loaded in Ca₃(PO₄)₂ oligomers. This general strategy can be used for other inorganic oligomer-based molecular switches and sensing systems.
- inorganic oligomer,
- photochromic,
- gels,
- naked-eye detection of hydrazine
1. [1]
  Zhang, X.; Zhang, J.; Ying, Y. L.; Tian, H.; Long, Y. T. Single molecule analysis of light-regulated RNA: spiropyran interactions. Chem. Sci. 2014, 5, 2642-2646. doi: 10.1039/c4sc00134f
2. [2]
  Wang, J. X.; Li, C.; Tian, H. Energy manipulation and metal-assisted photochromism in photochromic metal complex. Coord. Chem. Rev. 2021, 427, 213579. doi: 10.1016/j.ccr.2020.213579
3. [3]
  Julià-López, A.; Hernando, J.; Ruiz-Molina, D.; González-Monje, P.; Sedó, J.; Roscini, C. Temperature-controlled switchable photochromism in solid materials. Angew. Chem. Int. Ed. 2016, 55, 15044-15048. doi: 10.1002/anie.201608408
4. [4]
  Euchler, D.; Ehgartner, C. R.; Hüsing, N.; Feinle, A. Monolithic spiropyran-based porous polysilsesquioxanes with stimulus-responsive properties. ACS Appl. Mater. Interfaces 2020, 12, 47754-47762. doi: 10.1021/acsami.0c14987
5. [5]
  Yang, R.; Ren, X.; Mei, L.; Pan, G.; Li, X.; Wu, Z.; Zhang, S.; Ma, W.; Yu, W.; Fang, H. Reversible three-color fluorescence switching of an organic molecule in the solid state via "pump-trigger" optical manipulation. Angew. Chem. Int. Ed. 2022.
6. [6]
  Julià-López, A.; Ruiz-Molina, D.; Hernando, J.; Roscini, C. Solid materials with tunable reverse photochromism. ACS Appl. Mater. Interfaces 2019, 11, 11884-11892.
7. [7]
  Gao, Y.; Yin, Q.; Geng, X.; Zhang, X.; Li, W.; Gao, Y.; Geng, X.; Zhang, X.; Li, W. Synthesis and photochromic behavior of comb-like acrylate polymer nanoparticle containing spiropyran. Dyes Pigments 2021, 189, 109237. doi: 10.1016/j.dyepig.2021.109237
8. [8]
  Abdollahi, A.; Sahandi-Zangabad, K.; Roghani-Mamaqani, H. Rewritable anticounterfeiting polymer inks based on functionalized stimuliresponsive latex particles containing spiropyran photoswitches: reversible photopatterning and security marking. ACS Appl. Mater. Interfaces 2018, 10, 39279-39292.
9. [9]
  Qiu, W.; Gurr, P. A.; Qiao, G. G. Color-switchable polar polymeric materials. ACS Appl. Mater. Interfaces 2019, 11, 29268-29275. doi: 10.1021/acsami.9b09023
10. [10]
  Williams, D. E.; Martin, C. R.; Dolgopolova, E. A.; Swifton, A.; Godfrey, D. C.; Ejegbavwo, O. A.; Pellechia, P. J.; Smith, M. D.; Shustova, N. B. Flipping the switch: fast photoisomerization in a confined environment. J. Am. Chem. Soc. 2018, 140, 7611-7622. doi: 10.1021/jacs.8b02994
11. [11]
  Kremer, S.; Ober, I.; Greussing, V.; Kopacka, H.; Gallmetzer, H. G.; Trubenbacher, B.; Demmel, D.; Olthof, S.; Huppertz, H.; Schwartz, H. A. Modulating the optical characteristics of spiropyran@metal-organic framework composites as a function of spiropyran substitution. Langmuir 2021, 37, 7834-7842. doi: 10.1021/acs.langmuir.1c01187
12. [12]
  Rice, A. M.; Martin, C. R.; Galitskiy, V. A.; Berseneva, A. A.; Leith, G. A.; Shustova, N. B. Photophysics modulation in photoswitchable metalorganic frameworks. Chem. Rev. 2020, 120, 8790-8813. doi: 10.1021/acs.chemrev.9b00350
13. [13]
  Liang, H. Q.; Guo, Y.; Shi, Y.; Peng, X.; Liang, B.; Chen, B. A light-responsive metal-organic framework hybrid membrane with high on/off photoswitchable proton conductivity. Angew. Chem. Int. Ed. 2020, 59, 7732-7737. doi: 10.1002/anie.202002389
14. [14]
  Garg, S.; Schwartz, H.; Kozlowska, M.; Kanj, A. B.; Müller, K.; Wenzel, W.; Ruschewitz, U.; Heinke, L. Lichtinduziertes Schalten der Leitfähigkeit von MOFs mit eingelagertem Spiropyran. Angew. Chem. 2019, 131, 1205-1210. doi: 10.1002/ange.201811458
15. [15]
  Kundu, P. K.; Olsen, G. L.; Kiss, V.; Klajn, R. Nanoporous frameworks exhibiting multiple stimuli responsiveness. Nat. Commun. 2014, 5, 1-9.
16. [16]
  Martin, C. R.; Park, K. C.; Corkill, R. E.; Kittikhunnatham, P.; Leith, G. A.; Mathur, A.; Abiodun, S. L.; Greytak, A. B.; Shustova, N. B. Photo-responsive frameworks: energy transfer in the spotlight. Faraday Discuss. 2021, 231, 266-280.
17. [17]
  Mohan Raj, A.; Raymo, F. M.; Ramamurthy, V. Reversible disassembly-assembly of octa acid-guest capsule in water triggered by a photochromic process. Org. Lett. 2016, 18, 1566-1569. doi: 10.1021/acs.orglett.6b00405
18. [18]
  Zhang, X. F.; Ma, X.; Hou, T.; Guo, K.; Yin, J.; Wang, Z.; Shu, L.; He, M.; Yao, J. Inorganic salts induce thermally reversible and anti-freezing cellulose hydrogels. Angew. Chem. Int. Ed. 2019, 58, 7366-7370. doi: 10.1002/anie.201902578
19. [19]
  Zhang, H.; Dasbiswas, K.; Ludwig, N. B.; Han, G.; Lee, B.; Vaikuntanathan, S.; Talapin, D. V. Stable colloids in molten inorganic salts. Nature 2017, 542, 328-331.
20. [20]
  El Sayed, S.; Pascual, L. S.; Licchelli, M.; Martínez-Máñez, R.; Gil, S.; Costero, A. M.; Sancenón, F. l. Chromogenic detection of aqueous formaldehyde using functionalized silica nanoparticles. ACS Appl. Mater. Interfaces 2016, 8, 14318-14322.
21. [21]
  Wang, Z.; Wang, W.; Sun, G.; Yu, D. Designed ionic microchannels for ultrasensitive detection and efficient removal of formaldehyde in an aqueous solution. ACS Appl. Mater. Interfaces 2019, 12, 1806-1816.
22. [22]
  Bruemmer, K. J.; Green, O.; Su, T. A.; Shabat, D.; Chang, C. J. Chemiluminescent probes for activity-based sensing of formaldehyde released from folate degradation in living mice. Angew. Chem. Int. Ed. 2018, 57, 7508-7512.
23. [23]
  Ma, X.; Tang, K. l.; Lu, K.; Zhang, C.; Shi, W.; Zhao, W. Structural engineering of hollow microflower-like CuS@C hybrids as versatile electrochemical sensing platform for highly sensitive hydrogen peroxide and hydrazine detection. ACS Appl. Mater. Interfaces 2021, 13, 40942-40952.
24. [24]
  Vernot, E. H.; MacEwen, J. D.; Bruner, R. H.; Haun, C. C.; Kinkead, E. R.; Prentice, D. E.; Hall Iii, A.; Schmidt, R. E.; Eason, R. L.; Hubbard, G. B. Long-term inhalation toxicity of hydrazine. Fundam. Appl. Toxicol. 1985, 5, 1050-1064.
25. [25]
  Liu, Z.; Shao, C.; Jin, B.; Zhang, Z.; Zhao, Y.; Xu, X.; Tang, R. Crosslinking ionic oligomers as conformable precursors to calcium carbonate. Nature 2019, 574, 394-398.
26. [26]
  Keyvan Rad, J.; Ghomi, A. R.; Karimipour, K.; Mahdavian, A. R. Progressive readout platform based on photoswitchable polyacrylic nanofibers containing spiropyran in photopatterning with instant responsivity to acid-base vapors. Macromolecules 2020, 53, 1613-1622.
27. [27]
  Qiu, X.; Ivasyshyn, V.; Qiu, L.; Enache, M.; Dong, J.; Rousseva, S.; Portale, G.; Stöhr, M.; Hummelen, J. C.; Chiechi, R. C. Thiol-free selfassembled oligoethylene glycols enable robust air-stable molecular electronics. Nat. Mater. 2020, 19, 330-337.
28. [28]
  Grissa, R.; Abramova, A.; Tambio, S. J.; Lecuyer, M.; Deschamps, M.; Fernandez, V.; Greneche, J. M.; Guyomard, D.; Lestriez, B.; Moreau, P. Thermomechanical polymer binder reactivity with positive active materials for Li metal polymer and Li-ion batteries: an XPS and XPS imaging study. ACS Appl. Mater. Interfaces 2019, 11, 18368-18376.
29. [29]
  Lu, Y.; Cai, Y.; Zhang, Q.; Ni, Y.; Zhang, K.; Chen, J. Rechargeable K-CO₂ batteries with a KSn anode and a carboxyl-containing carbon nanotube cathode catalyst. Angew. Chem. Int. Ed. 2021, 60, 9540-9545.
30. [30]
  Eckhardt, H.; Bose, A.; Krongauz, V. A. Formation of molecular H- and J-stacks by the spiropyran-merocyanine transformation in a polymer matrix. Polymer 1987, 28, 1959-1964.
31. [31]
  Nakamura, M.; Fujioka, T.; Sakamoto, H.; Kimura, K. High stability constants for multivalent metal ion complexes of crown ether derivatives incorporating two spirobenzopyran moieties. New J. Chem. 2002, 26, 554-559.
32. [32]
  Tanaka, M.; Ikeda, T.; Xu, Q.; Ando, H.; Shibutani, Y.; Nakamura, M.; Sakamoto, H.; Yajima, S.; Kimura, K. Synthesis and photochromism of spirobenzopyrans and spirobenzothiapyran derivatives bearing monoazathiacrown ethers and noncyclic analogues in the presence of metal ions. J. Org. Chem. 2002, 67, 2223-2227.
33. [33]
  Lin, S.; Ruan, Y. Z.; Shen, Y.; Luo, J. R. Crystalline phase and decomposition dynamics of aluminum titanate at different temperature. Chin. J. Struct. Chem. 2012, 31, 79-84.
34. [34]
  Abdollahi, A.; Roghani-Mamaqani, H.; Razavi, B.; Salami-Kalajahi, M. Photoluminescent and chromic nanomaterials for anticounterfeiting technologies: recent advances and future challenges. ACS Nano 2020, 14, 14417-14492.
35. [35]
  Li, X.; Xu, S.; Liu, F.; Qu, J.; Shao, H.; Wang, Z.; Cui, Y.; Ban, D.; Wang, C. Bi and Sb codoped Cs₂Ag_0.1Na_0.9InCl₆ double perovskite with excitation-wavelength-dependent dual-emission for anti-counterfeiting application. ACS Appl. Mater. Interfaces 2021, 13, 31031-31037.
36. [36]
  Wang, F.; Gerken, J. B.; Bates, D. M.; Kim, Y. J.; Stahl, S. S. Electrochemical strategy for hydrazine synthesis: development and overpotential analysis of methods for oxidative N-N coupling of an ammonia surrogate. J. Am. Chem. Soc. 2020, 142, 12349-12356.
37. [37]
  Jia, Y.; Shang, N.; He, X.; Nsabimana, A.; Gao, Y.; Ju, J.; Yang, X.; Zhang, Y. Electrocatalytically active cuprous oxide nanocubes anchored onto macroporous carbon composite for hydrazine detection. J. Colloid Interface Sci. 2022, 606, 1239-1248.
38. [38]
  García-Aldea, D.; Alvarellos, J. E. Generalized nonlocal kinetic energy density functionals based on the von Weizsäcker functional. PCCP 2012, 14, 1756-1767.
39. [39]
  Li, J.; Yim, D.; Jang, W. D.; Yoon, J. Recent progress in the design and applications of fluorescence probes containing crown ethers. Chem. Soc. Rev. 2017, 46, 2437-2458.
40. [40]
  Feller, D.; Bross, D. H.; Ruscic, B. Enthalpy of formation of N₂H₄ (hydrazine) revisited. J. Phys. Chem. A 2017, 121, 6187-6198.
41. [41]
  Fabiano, B.; Reverberi, A. P.; Varbanov, P. S. Safety opportunities for the synthesis of metal nanoparticles and short-cut approach to workplace risk evaluation. J. Clean. Prod. 2019, 209, 297-308.
42. [42]
  Liu, T.; Yang, L. J.; Feng, W.; Liu, K.; Ran, Q.; Wang, W.; Liu, Q.; Peng, H.; Ding, L.; Fang, Y. Dual-mode photonic sensor array for detecting and discriminating hydrazine and aliphatic amines. ACS Appl. Mater. Interfaces 2020, 12, 11084-11093.
43. [43]
  Kong, X.; Li, M.; Zhang, Y.; Yin, Y.; Lin, W. Engineering an AIE N₂H₄ fluorescent probe based on α-cyanostilbene derivative with large Stokes shift and its versatile applications in solution, solid-state and biological systems. Sens. Actuators B Chem. 2021, 329, 129232.
44. [44]
  Guo, T.; Wu, J.; Gao, H.; Chen, Y. Covalent functionalization of multi-walled carbon nanotubes with spiropyran for high solubility both in water and in non-aqueous solvents. Inorg. Chem. Commun. 2017, 83, 31-35.
45. [45]
  Ozhogin, I. V.; Chernyavina, V. V.; Lukyanov, B. S.; Malay, V. I.; Rostovtseva, I. A.; Makarova, N. I.; Tkachev, V. V.; Lukyanova, M. B.; Metelitsa, A. V.; Aldoshin, S. M. Synthesis and study of new photochromic spiropyrans modified with carboxylic and aldehyde substituents. J. Mol. Struct. 2019, 1196, 409-416.
46. [46]
  Goswami, S.; Aich, K.; Das, S.; Das, A. K.; Sarkar, D.; Panja, S.; Mondal, T. K.; Mukhopadhyay, S. A red fluorescence 'off-on' molecular switch for selective detection of Al³⁺, Fe³⁺ and Cr³⁺: experimental and theoretical studies along with living cell imaging. Chem. Commun. 2013, 49, 10739-10741.
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