Behavior of fullerene C70 in binary organic solvent mixtures as studied using UV-Vis spectra and dynamic light scattering

Keywords: fullerene C70, toluene, n-hexane, acetonitrile, methanol, molecular solutions, organosol, UV visible absorption spectra, dynamic light scattering, particle size

Abstract

In this paper, the formation of colloidal species of fullerene C70 in organic solvents was studied. The examining of the UV-visible spectra was accompanied by particle size analysis using dynamic light scattering, DLS. Stock solutions of C70 in non-polar toluene and n-hexane were diluted with polar solvents acetonitrile and methanol. The appearance of colloidal species with a size within the range of ≈50–500 nm is accompanied by alterations of the absorption spectra.

In the toluene–acetonitrile and toluene–methanol binary mixed solvents at 25 oC, the absorption spectra of C70 (5×10–6 M) tend to retain the features of the spectrum in neat aromatic solvent even if the C70 molecules are gathered into colloidal aggregates. Earlier such phenomenon was observed for C60 in benzene–acetonitrile and toluene–methanol solvent systems. This gives support to the idea of rather stable primary solvate shells formed by aromatic molecules around the fullerene molecules. The behavior of C70 in toluene mixtures with methanol was compared with the earlier reported results from this laboratory for the C60 fullerene in the same solvent system.

The study of n-hexane–methanol mixtures was performed at elevated temperature because of limited miscibility of these solvents at 25 oC. Accordingly, the C70–toluene–methanol system was also examined at 40 oC. A small but distinctly noticeable difference was revealed. Whereas in the case of the last-named system, the absorption spectrum typical for molecular form of C70 is still observable when colloidal species are already present in the solution, the turning-point between molecules and colloids as determined by both UV-visible spectra and DLS coincides for the n-hexane–methanol binary mixed solvent. Hence, the solvation shells formed by the aliphatic solvent around C70 are less stable as compared with those formed by toluene.

Finally, the absorption spectra of C70 in the mixed solvents toluene–n-hexane were analyzed. These data give some support to the assumption of preferable solvation of the C70 molecules by the aromatic co-solvent.

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References

Ruoff R.S., Tse D.S., Malhotra R., Lorents D.C. Solubility of C60 in a variety of solvents. J. Phys. Chem. 1993, 97(13), 3379-3383.

Marcus Y. Solubilities of buckminsterfullerene and sulfur hexafluoride in various solvents. J. Phys. Chem. 1997, 101(42) 8617-8623.

Beck M.T. Solubility and molecular state of C60 and C70 solvents and solvent mixtures. Pure Appl. Chem. 1998, 70(10), 1881-1887.

Marcus Y., Smith A.L., Korobov M.V., Mirakyan A. L., Avramenko N. V., Stukalin E.B. Solubility of C60 fullerene. J. Phys. Chem.B 2001, 105(13), 2499-2506.

Kinchin A.N., Kolker A.M., Islamova N.I. Correlations between the thermodynamic parame-ters of solution of fullerene C60 and the properties of nonaqueous solvents. (in Russian). Zhurn. Fiz. Khim. 2002, 76(10), 1772-1776.

Semenov K.N., Charykov N.A., KeskinovV.A., Piartman A.K., Blokhin A.A., Kopyrin A.A. Solubility of light fullerenes in organic solvents. J. Chem. Eng. Data. 2010, 55(1), 13-36.

Avdeev M.V., Aksenov V.L., Tropin T.V. Models of cluster formation in solutions of fullere-nes. Russ. J. Phys. Chem. A 2010, 84(8), 1273-1283.

Mchedlov-Petrossyan N.O. Fullerenes in Liquid Media: An Unsettling Intrusion into the Solu-tion Chemistry. Chem. Rev. 2013, 113(7), 5149-5193.

Aksenov V.L., Avdeev M.V., Tropin T.V., Priezzhev V.B., Schmelzer J.W.P. Cluster growth and dissolution of fullerenes in non-polar solvents. J. Mol. Liquids. 2006, 127, 142-144.

Sun Y.-P., Bunker C.E. C70 in solvent mixtures. Nature, 1993, 365, 398.

Sun Y.-P., Bunker C.E. Formation and Properties of C7O Solidlike Species in Room-Temperature Solutions. Chem. Mater. 1994, 6(5), 578-580.

Sun Y.-P., Ma B., Bunker C.E., Liu B. All-Carbon Polymers (Polyfullerenes) from Photo-chemical Reactions of Fullerene Clusters in Room-Temperature Solvent Mixtures. J. Am. Chem. Soc. 1995, 117(51), 12705-12711.

Ghosh H.N., Sapre A.V., Mittal J.P. Aggregation of C70 in Solvent Mixtures. J. Phys. Chem. 1996, 100(22), 9439-9443.

Rudalevige T., Francis A.H., Zand R. Spectroscopic studies of fullerene aggregates. J. Phys. Chem. A. 1998, 102(48), 9797-9802.

Alargova R.G., Deguchi S., Tsujii K. Stable Colloidal Dispersions of Fullerenes in Polar Or-ganic Solvents. J. Am. Chem. Soc. 2001, 123(43), 10460-10467.

Alfe M. Alfe, B. Apicella, R. Barbella, A. Bruno, A. Ciajolo. Aggregation and interactions of C60 and C70 fullerenes in neat N-methylpyrrolidinone and in N-methylpyrrolidinone/toluene mixtures. Chem. Phys. Lett. 2005, 405, 193-197.

Nagorna T.V., Kuzmenko M.O., Kyzyma O.A., Chudoba D., Nagornyi A.V., Tropin T.V., Garamus V.M., Jazdzewska M., Bulavin L.A. Structural reorganization of fullerene C70 in N methyl-2-pyrrolidone / toluene mixtures. J. Mol. Liquids. 2018, 272, 948-952.

Nath S., Pal H., Nath A.V.S., Pal H., Sapre A.V. Effect of solvent polarity on the aggregation of C60. Chem. Phys. Lett. 2000, 327, 143-148.

Nath S., Pal H., Sapre A.V., Effect of solvent polarity on the aggregation of fullerenes: a com-parison between C60 and C70. Chem. Phys. Lett. 2002, 360, 422-428.

Mchedlov-Petrossyan N.O., Kamneva N.N., Al-Shuuchi Y.T.M., Marynin A.I., Shekhovtsov S.V. The peculiar behavior of fullerene C60 in mixtures of ‘good’ and polar solvents: Colloidal particles in the toluene–methanol mixtures and some other systems. Colloids Surfaces A. 2016, 509, 631-637.

Mchedlov-Petrossyan N.O., Kamneva N.N., Al-Shuuchi Y.T.M., Marynin A.I., Zozulia O.S. Formation and ageing of the fullerene C60 colloids in polar organic solvents. J. Mol. Liquids. 2017, 235, 98-103.

Chamberlain T.W., Popov A.M., Knizhnik A.A., Samoilov G.E., Khlobystov A.N. The role of molecular clusters in the filling of carbon nanotubes. ACS NANO 2010, 4(9), 5203-5210.

Ginzburg B.M., Tuĭchiev Sh. Variations in the structure of aromatic solvents under the influ-ence of dissolved fullerene C70. Crystallogr. Rep. 2008, 53(4), 645-650.

Ginzburg B.M., Tuĭchiev Sh., Shukhiev S. Permittivity of Low_Concentration C60 Fullerene Solutions in p_Xylene. Tech. Phys. Lett. 2009, 35(6), 491-493.

Ginzburg, B. M.; Tuĭchiev, Sh.; Tabarov, S. Kh. Effect of C60 Fullerene on the Boiling Point of Its Solutions in Some Aromatic SolventsRuss. J. Appl. Chem. 2009, 82(3), 387–390.

Ginzburg B.M., Tuichiev Sh., Yakimanskii A.V. Supramolecular Benzene Structure and Its Changes under the Action of Dissolved Fullerenes. Crystallogr. Rep. 2011, 56(2), 238-241.

Ginzburg B.M., Tuichiev Sh., Rashidov D., Sodikov F.H., Tabarov S.H., Shepelevskii A.A. Step-Wise Concentration Influence of Fullerenes C60 and C70 on the Various Parameters of Condensed Systems. Part 1: The Concept of Step-Wise Behavior and its Manifestation in Fullerene Solutions. J. Macromol. Sci., Part B: Physics. 2015, 54, 533-543.

Cataldo F., Iglesias-Groth S., Hafez Y. On the molar extinction coefficients of the electronic absorption spectra of C60 and C70 fullerenes radical cation. Eur. Chem. Bull. 2013, 2(12), 1013 1018.

Mchedlov-Petrossyan N.O., Kamneva N.N., Al-Shuuchi Y.T.M., Marynin A.I. , Zozulia O.S., Kryshtal A.P., Klochkov V.K., Shekhovtsov S.V. Towards better understanding of C60 or-ganosols. Phys. Chem. Chem. Phys. 2016, 18, 2517-2526.

Volmer M. Kinetik der Phasenbildung (Russian translation), Nauka, Moscow, 1986, Ch. 5.

Semenov I.A., Sitnikov D.N., Romanovskiy A.A., Ulyanov B.A. Solubility and equuiliria in bimary mixtures of methanol with n-pentane, n-hexane, and n-heptane. (in Russian). Izvestiya Vusov. Khim. I Khim. Technol. 2012, 55(8), 39-42.

Published
2019-12-27
Cited
0 article
How to Cite
Marfunin, N., & Mchedlov-Petrossyan, N. (2019). Behavior of fullerene C70 in binary organic solvent mixtures as studied using UV-Vis spectra and dynamic light scattering. V. N. Karazin Kharkiv National University Bulletin. Chemical Series, (33), 77-87. https://doi.org/10.26565/2220-637X-2019-33-06

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