Photoluminescent Registration of New Substances Based on Fullerite C₆₀ Obtained by Chemical Interaction with H₂ and N₂ Molecules

Abstract:

Polycrystalline C₆₀ saturated with molecular hydrogen and nitrogen were studied using the spectral-luminescent method of registration in the quantum counting mode at a low temperature of 20 K. Previously, it was found that the temperature limit of the adsorption crossover (the transition from the diffusion mechanism of intercalation - physisorption to chemical interaction - chemisorption) for fullerite C₆₀ in an H₂ atmosphere is about 250 °C [1], and in an N₂ atmosphere – 420 °C [2], respectively. At saturation temperatures above those indicated, the process of chemical interaction of impurity molecules and the fullerite matrix occurs with the formation of new compounds. Therefore, saturation was carried out at temperatures of 300 °C for hydrogen and 450 °C for nitrogen under a pressure of 30 atm. For the first time, the results of registration of photoluminescent radiation at low temperatures from new substances based on fullerite C₆₀ are presented. A mixture of weakly saturated fulleranes C₆₀H_X was obtained by saturation of hydrogen from the gas phase at a temperature close to the sorption crossover temperature, and their low-temperature photoluminescence was identified for the first time. The analysis of the "blue" shift of the beginning of the spectrum of such radiation allowed us to more accurately attribute the obtained material to the initial segment of the fullerane series. The presence of radiation of the azafullerene dimer (biazafullerene) (C₅₉N)₂ in the spectra of the reaction products of C₆₀ with N₂ was also detected. It was shown that for polycrystalline samples of C₆₀ saturated in a nitrogen atmosphere, the characteristic luminescence of biazafullerene with a maximum at 1.53 eV determines the intensity and shape of the entire short-wave part of the emission spectrum of the complex of synthesized substances.

• Periodical: Materials Science Forum (Volume 1179)
• Pages: 19-27
• DOI: https://doi.org/10.4028/p-6mu6Vx
• Online since: March 2026
• Authors: Viktor Zoryansky*, Peter Zinoviev, Yuri Semerenko
• Keywords: Adsorption Crossover, Biazafullerene (C₅₉N)₂, C₆₀H₃₆, Electronic Excitations, Fullerite C₆₀, H2 and N2 Saturation, HOMO-LUMO Gape, Hydrofullerene C₆₀H_X, Photoluminescence Spectrum

References

[1] A. B. Harris and R. Sachidanandam, Orientational ordering of icosahedra in solid C60, Phys. Rev. B 46 (1992) 4944–4957

DOI: 10.1103/PhysRevB.46.4944

[2] S. A. FitzGerald, T. Yildirim, L. J. Santodonato, D. A. Neumann, J. R. D. Copley, J. J. Rush, and F. Trouw, Quantum dynamics of interstitial H2 in solid C60, Phys. Rev. B 60 (1999) 6439-6451

DOI: 10.1103/PhysRevB.60.6439

[3] G. E. Gadd, P. J. Evans, S. Moricca and M. James, The intercalation of Ar into C60 films, Journal of Materials Research ,12 (1997) 1-4

DOI: 10.1557/JMR.1997.0001

[4] B. P. Uberuaga, A. F. Voter, K. K. Sieber, and D. S. Sholl, Mechanisms and rates of interstitial H2 diffusion in crystalline C60, Phys. Rev. Lett. 91 (2003) 105901

DOI: 10.1103/PhysRevLett.91.105901

[5] A. I. Prokhvatilov, N. N. Galtsov, I. V. Legchenkova, M. A. Strzhe mechny, D. Cassidy, G. E. Gadd, S. Moricca, B. Sundqvist, and N. A. Aksenova, Hysteretic phenomena in Xe-doped from X-ray diffraction, Low Temp. Phys. 31 (2005) 445-448

DOI: 10.1063/1.1925372

[6] M. S. Dresselhaus, G. Dresselhaus, and P. C. Eklund, Science of Fullerenes and Carbon Nanotubes, Academic Press, San Diego (1996)

DOI: 10.1002/adma.19970091518

[7] Vergara-Reyes, H. N., Acosta-Alejandro, M. & Chigo-Anota, E. Quantum-mechanical assessment of the adsorption of nitric oxide molecules on the magnetic carbon nitride (C36N24)−fullerene. Struct. Chem. 32 (2021) 1775–1786

DOI: 10.1007/s11224-021-01736-8

[8] Jia, R., Yang, X., Li, H., Jin, B. & Xu, K. Interaction between cis-2 bis(benzofuro)[60]fullerene derivative and gas molecules of energetic materials (NO, NO2, N2, CO, CO2 and HCN): A DFT-D study. Computational and Theoretical Chemistry, 1212 (2022) 113690

DOI: 10.1016/j.comptc.2022.113690

[9] Omid Moztarzadeh, Morteza Jamshidi, Avat Arman Taherpour, Vaclav Babuska, Molecular modelling of fullerene C60 functionalized by nitric oxide for use in biological environment, Scientific Reports, 14 (2024) 2565

DOI: 10.1038/s41598-024-53050-y

[10] K.A. Yagotintsev, I.V. Legchenkova, Yu.E. Stetsenko, P.V. Zinoviev, V.N. Zoryansky, A.I. Prokhvatilov, and M.A. Strzhemechny, Saturation of fullerite C60 with hydrogen: Adsorption crossover studies, Low Temp. Phys. 38 (2012) 952–956

DOI: 10.1063/1.4758781

[11] I.V. Legchenkova, K.A. Yagotintsev, N.N. Galtsov, V.V. Meleshko, Yu.E. Stetsenko, and A.I. Prokhvatilov, Effect of nitrogen sorption mechanisms on the properties of fullerite C60 over a wide range of temperatures, Low Temp. Phys. 40 (2014) 685-689

DOI: 10.1063/1.4894316

[12] P.V. Zinoviev, V.N. Zoryansky, N.B. Silaeva, Yu.E. Stetsenko, M.A. Strzhemechny, and K.A. Yagotintsev, Orientational glassification in fullerite C60 saturated with H2: Photoluminescence studies, Low Temp. Phys. 38 (2012) 732-739

DOI: 10.1063/1.4746795

[13] Yu.E. Stetsenko, I.V. Legchenkova, K.A. Yagotintsev, A.I. Prokhvatilov, and M.A. Strzhemechnyı, Intercalation of C60 fullerite with helium and argon at normal temperature and pressure, Low Temp. Phys. 29 (2003)] 445-448

DOI: 10.1063/1.1542509

[14] G.E. Gadd, S. Moricca, S.J. Kennedy, M.M. Elcombe, P.J. Evans, M. Blackford., D. Cassidy, C.J. Howard, P. Prasad, J.V. Hanna, A. Burchwood, and D. Lavy, Novel rare gas interstitial fullerenes of C60 with Ar, Kr and Xe, J. Phys. Chem. Solids 58 (1997) 1823-1832

DOI: 10.1016/S0022-3697(97)00096-6

[15] P.V. Zinoviev, V.N. Zoryansky, Photoluminescence of C60 fullerite intercalated with nitrogen molecules wide range of temperatures, Low Temp. Phys. 48 (2022) 268-270

DOI: 10.1063/10.0009547

[16] I. Akimoto and K. Kan'no, Photoluminescence and Near-Edge Optical Absorption in the Low-Temperature Phase of Pristine C60 Single Crystals, J. Phys. Soc. Jpn. 71 (2002) 630-643

DOI: 10.1143/JPSJ.71.630

[17] P.V. Zinoviev, V.N. Zoryansky, N.B.  Silaeva, Photoluminescence of C60 single crystals intercalated with molecular hydrogen, Low Temp. Phys. 34 (2008) 484-486

DOI: 10.1063/1.2920183

[18] P.V. Zinoviev, V.N. Zoryansky, V.V. Meleshko, Yu.E. Stetsenko, Effect of molecular nitrogen impurity on the photoluminescence of fullerite C60, Low Temp. Phys. 41 (2015) 236-238

DOI: 10.1063/1.4915916

[19] K.P. Meletov, G.A. Kourouklis, High-pressure hydrogenated fullerenes: Optical spectra and stability of C60H36 at high pressure, J. Exp. Theor. Phys. 100 (2005) 760-774

DOI: 10.1134/1.1926437

[20] J.A. Teprovich, Jr., A.L. Washington, II, J. Dixon, P.A. Ward, J.H. Christian, B. Peters, J. Zhou, S. Giri, D.N. Sharp, J.A. Velten, R.N. Compton, P. Jenab, R. Zidan, Investigation of hydrogen induced fluorescence in C60 and its potential use in luminescence down shifting applications, Nanoscale 44 (2016) 18760-18770

DOI: 10.1039/c6nr05998h

[21] B. Ma, A. Weitz, F. Wudl, The photophyiscal properties of azafullerenes C59HN and its dimer (C59N)2, Proc. Electrochem. Soc. 12 (1999) 359-367