Photoluminescent porous aerogel monoliths containing ZnEu-complex: the first example of aerogel modified with a heteronuclear metal complex

  • Kh. E. Yorov
  • S. Yu. Kottsov
  • А. Е. Baranchikov
  • O. V. Boytsova
  • M. A. Kiskin
  • E. A. Varaksina
  • G. P. Kopitsa
  • S. А. Lermontov
  • A. A. Sidorov
  • V. Pipich
  • A. Len
  • A. V. Agafonov
  • V. K. IvanovEmail author
Original Paper: Nano- and macroporous materials (aerogels, xerogels, cryogels, etc.)


A procedure for the chemical immobilization of a new ZnII–EuIII heterobimetallic complex in the SiO2 aerogel matrix has been developed. In this Zn–Eu complex, a peripheral non-luminescent Zn ion acts as a binder to a silica matrix and prevents direct interaction of rare-earth ions with OH− and NH− groups in the silica matrix, which would have a detrimental effect on the luminescence of lanthanides. The procedure includes the synthesis of complexes, co-gelation of the obtained complex with SiO2 sol, the washing of lyogels, and their subsequent supercritical drying in CO2. The composition and properties of the obtained aerogels were investigated using a low-temperature nitrogen adsorption technique, helium pycnometry, FTIR, Raman, UV–visible, and luminescence spectroscopy, XPS, PXRD, SEM, TEM, TGA combined with mass spectrometry, and small-angle neutron scattering. The aerogels modified with the ZnII–EuIII complex demonstrated strong red luminescence upon excitation with UV light.


  • An approach is proposed for anchoring heterobimetallic complexes to silica aerogel matriх.

  • In anchored complex, Zn atoms shield Eu from luminescence quenchers.

  • Silica aerogel modified with Zn–Eu complex demonstrated strong red luminescence.


Aerogel Heteronuclear metal complex Silica Luminescence Structure 



The authors are grateful to S.R. Kiraev (Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Moscow, Russia) for assistance in the synthesis of the initial complexes, T.B. Shatalova (Lomonosov Moscow State University) for assistance in conducting thermal analysis of samples, L.A. Azarova (B.P. Konstantinov St. Petersburg Nuclear Physics Institute, Gatchina, Russia) and N.V. Tsvigun (IFSRC “Crystallography and Photonics” of the Russian Academy of Sciences, Moscow, Russia) for assistance in measuring USANS and SANS, and T.B. Khamova (Grebenshchikov Institute of Silicate Chemistry of the Russian Academy of Sciences, St. Petersburg, Russia) for assistance in nitrogen adsorption on aerogel samples. This work was supported by the Russian Foundation for Basic Research (Project Nos. 18-29-06014 and 16-29-10736). Investigations were carried out using the equipment of the Joint Research Center for Physical Methods of Research of Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences. M. Kiskin thanks VolkswagenStiftung, Trilateral Partnership project “Multifunctional molecular materials—bridging magnetism and luminescence”.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10971_2019_4958_MOESM1_ESM.docx (1.4 mb)
Supplementary Information


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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Kh. E. Yorov
    • 1
  • S. Yu. Kottsov
    • 2
    • 3
  • А. Е. Baranchikov
    • 3
  • O. V. Boytsova
    • 1
    • 3
  • M. A. Kiskin
    • 3
  • E. A. Varaksina
    • 4
    • 5
  • G. P. Kopitsa
    • 6
    • 7
  • S. А. Lermontov
    • 8
  • A. A. Sidorov
    • 3
  • V. Pipich
    • 9
  • A. Len
    • 10
  • A. V. Agafonov
    • 11
    • 12
  • V. K. Ivanov
    • 3
    • 11
    Email author
  1. 1.Lomonosov Moscow State UniversityMoscowRussia
  2. 2.Dmitry Mendeleev University of Chemical Technology of RussiaMoscowRussia
  3. 3.Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of SciencesMoscowRussia
  4. 4.Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of SciencesMoscowRussia
  5. 5.Lebedev Physical Institute of the Russian Academy of SciencesMoscowRussia
  6. 6.Petersburg Nuclear Physics Institute of National Research Centre “Kurchatov Institute”St. PetersburgRussia
  7. 7.Grebenshchikov Institute of Silicate Chemistry of the Russian Academy of SciencesSt. PetersburgRussia
  8. 8.Institute of Physiologically Active Compounds of the Russian Academy of SciencesChernogolovkaRussia
  9. 9.Jülich Centre for Neutron ScienceForschungszentrum Jülich GmbHGarchingGermany
  10. 10.Wigner Research Centre for PhysicsInstitute for Solid State Physics and OpticsBudapestHungary
  11. 11.National Research Tomsk State UniversityTomskRussia
  12. 12.Krestov Institute of Solution Chemistry of the Russian Academy of SciencesIvanovoRussia

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