Skip to main content
Log in

Synthesis of azobenzene-containing macrocycles exhibiting unexpected fluorescence

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

Polyfunctional macrocycles have been studied extensively for their responsive properties. In this study, three electron- deficient novel azo-containing crown ethers were successfully synthesized. The synthesized macrocycles were characterized and their photophysical along with photoisomerization were studied. The results were compared with their acyclic derivative. It was found that these compounds did not convert to their cis-isomer completely due to the rigidity of the cycles. The fluorescence studies revealed that the macrocycles were fluorescent while the acyclic azo derivative was found not to show fluorescence. The macrocycles were also tested for alkali metal cation-binding abilities. It was shown with DFT calculations that not only the ring size of macrocycles but also the conformation places an important role in recognition of these cations.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

Data availability

The datasets generated during the current study is available from the corresponding author.

Code availability

Not applicable.

References

  • Antoine John A, Lin Q (2017) Synthesis of azobenzenes using N-chlorosuccinimide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). J Org Chem 82(18):9873–9876

    Article  CAS  Google Scholar 

  • Bandara HMD, Burdette SC (2012) Photoisomerization in Different classes of azobenzene. Chem Soc Rev 41(5):1809–1825

    Article  CAS  Google Scholar 

  • Crecca CR, Roitberg AE (2006) Theoretical study of the isomerization mechanism of azobenzene and disubstituted azobenzene derivatives. J Phys Chem A 110:8188–8203

    Article  CAS  Google Scholar 

  • Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision A.02. Gaussian, Inc., Wallingford, CT

    Google Scholar 

  • Geng WC, Sun H, Guo DS (2018) Macrocycles containing azo groups: recognition assembly and application. J Incl Phenom Macrocycl Chem 92:1–79

    Article  CAS  Google Scholar 

  • Gokel GW, Leevy WM, Weber ME (2004) Crown ethers: sensors for ions and molecular scaffolds for materials and biological models. Chem Rev 104(5):2723–2750

    Article  CAS  Google Scholar 

  • Griffiths J II (1972) Photochemistry of azobenzene and its derivatives. Chem Soc Rev 1(4):481–493

    Article  CAS  Google Scholar 

  • Heindl AH, Becker J, Wegner HA (2019) Selective switching of multiple azobenzenes. Chem Sci 10(31):7418–7425

    Article  CAS  Google Scholar 

  • Hyun MH (2016) Liquid chromatographic enantioseparations on crown ether-based chiral stationary phases. J Chromatogr A 1467:19–32

    Article  CAS  Google Scholar 

  • Merino E (2011) Synthesis of azobenzenes: the coloured pieces of molecular materials. Chem Soc Rev 40(7):3835–3853

    Article  CAS  Google Scholar 

  • Pedersen CJ (1967) Cyclic polyethers and their complexes with metal salts. J Am Chem Soc 89:2495–2496

    Article  CAS  Google Scholar 

  • Qu DH, Wang QC, Zhang QW, Ma X, Tian H (2015) Photoresponsive host-guest functional systems. Chem Rev 115(15):7543–7588

    Article  CAS  Google Scholar 

  • Rau H (1984) Further evidence for rotation in the π, π* and inversion in the n, π* photoisomerization of azobenzenes. J Photochem 26:221

    Article  CAS  Google Scholar 

  • Rau H, Lüddecke E (1982) On the rotation-inversion controversy on photoisomerization of azobenzenes. Experimental proof of inversion. J Am Chem Soc 104(6):1616–1620

    Article  CAS  Google Scholar 

  • Scriba GKE (2016) Chiral recognition in separation science. J Chromatogr A 1467:56–78

    Article  CAS  Google Scholar 

  • Shinkai S, Nakaji T, Ogawa T, Shigematsu K, Manabe O (1981) Photoresponsive crown ethers. 2. Photocontrol of ion extraction and ion transport by a bis(crown ether) with a butterfly-like motion. J Am Chem Soc 103(1):111–115

    Article  CAS  Google Scholar 

  • Szarmach M, Wagner-Wysiecka E, Fonari MS, Luboch E (2012) Bis(azobenzocrown ether)s—synthesis and ionophoric properties. Tetrahedron 68(2):507–515

    Article  CAS  Google Scholar 

  • Wagner-Wysiecka E, Łukasik N, Biernat JF, Luboch E (2018) Azo group(s) in selected macrocyclic compounds. J Incl Phenom Macrocycl Chem 90:189–257

    Article  CAS  Google Scholar 

  • Yoo C, Dodge HM, Miller AJM (2019) Cation-controlled catalysis with crown ether-containing transition metal complexes. Chem Commun 55(35):5047–5059

    Article  CAS  Google Scholar 

  • Yoshino J, Kano N, Kawashima T (2013) Fluorescent azobenzenes and aromatic aldimines featuring an N-B interaction. Dalt Trans 42:15826–15834

    Article  CAS  Google Scholar 

  • Yu J, Qi D, Li J (2020) Design, synthesis and applications of responsive macrocycles. Commun Chem 3(1):1–14

    Article  Google Scholar 

  • Zhang C, Jiao N (2010) Copper-catalyzed aerobic oxidative dehydrogenative coupling of anilines leading to aromatic azo compounds using dioxygen as an oxidant. Angew Chemie Int Ed 49(35):6174–6177

    Article  CAS  Google Scholar 

Download references

Funding

No funding support for the research.

Author information

Authors and Affiliations

Authors

Contributions

AA contributed to conception and design of the study. Material preparation, data collection and analysis were performed E.H and AA. All authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Corresponding author

Correspondence to Akin Akdag.

Ethics declarations

Conflict of interest

The author declares that there is no conflict of interest.

Ethics approval

Not applicable.

Consent to participate

Not applicable.

Consent for publication

Not applicable.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Hosgor, E., Akdag, A. Synthesis of azobenzene-containing macrocycles exhibiting unexpected fluorescence. Chem. Pap. 76, 3891–3898 (2022). https://doi.org/10.1007/s11696-022-02133-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11696-022-02133-z

Keywords

Navigation