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Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study.

ABSTRACT: Fullerenes attract much attention in various scientific fields, but their electronic properties are still not completely understood. Here we report on a combined EPR and DFT study of the fullerene anion C60- in solid glassy environment. DFT calculations were used to characterize its electronic structure through spin density distribution and magnetic resonance parameters. The electron spin density is not uniformly distributed throughout the C60- cage but shows a pattern similar to PC61BM-. EPR spectroscopy reveals a rhombic g-tensor sensitive to the environment in the frozen glassy solutions, which can be rationalized by deformation of the fullerenes along low-frequency vibrational modes upon cooling. DFT modeling confirms that these deformations lead to variation in the C60- g values. The decrease in g-tensor anisotropy with sample annealing is related to the lessening of g-tensor strain upon temperature relaxation of the most distorted sites in the glassy state.

SUBMITTER: Niklas J

PROVIDER: S-EPMC6563802 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study.

Niklas Jens J Mardis Kristy L KL Poluektov Oleg G OG

The journal of physical chemistry letters 20180703 14

Fullerenes attract much attention in various scientific fields, but their electronic properties are still not completely understood. Here we report on a combined EPR and DFT study of the fullerene anion C60- in solid glassy environment. DFT calculations were used to characterize its electronic structure through spin density distribution and magnetic resonance parameters. The electron spin density is not uniformly distributed throughout the C60- cage bu ...[more]

PMID: 29969036

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Project description:The ongoing depletion of fossil fuels has led to an intensive search for additional renewable energy sources. Solar-based technologies could provide sufficient energy to satisfy the global economic demands in the near future. Photovoltaic (PV) cells are the most promising man-made devices for direct solar energy utilization. Understanding the charge separation and charge transport in PV materials at a molecular level is crucial for improving the efficiency of the solar cells. Here, we use light-induced EPR spectroscopy combined with DFT calculations to study the electronic structure of charge separated states in blends of polymers (P3HT, PCDTBT, and PTB7) and fullerene derivatives (C60-PCBM and C70-PCBM). Solar cells made with the same composites as active layers show power conversion efficiencies of 3.3% (P3HT), 6.1% (PCDTBT), and 7.3% (PTB7), respectively. Upon illumination of these composites, two paramagnetic species are formed due to photo-induced electron transfer between the conjugated polymer and the fullerene. They are the positive, P(+), and negative, P(-), polarons on the polymer backbone and fullerene cage, respectively, and correspond to radical cations and radical anions. Using the high spectral resolution of high-frequency EPR (130 GHz), the EPR spectra of these species were resolved and principal components of the g-tensors were assigned. Light-induced pulsed ENDOR spectroscopy allowed the determination of (1)H hyperfine coupling constants of photogenerated positive and negative polarons. The experimental results obtained for the different polymer-fullerene composites have been compared with DFT calculations, revealing that in all three systems the positive polaron is distributed over distances of 40-60 Å on the polymer chain. This corresponds to about 15 thiophene units for P3HT, approximately three units for PCDTBT, and about three to four units for PTB7. No spin density delocalization between neighboring fullerene molecules was detected by EPR. Strong delocalization of the positive polaron on the polymer donor is an important reason for the efficient charge separation in bulk heterojunction systems as it minimizes the wasteful process of charge recombination. The combination of advanced EPR spectroscopy and DFT is a powerful approach for investigation of light-induced charge dynamics in organic photovoltaic materials.

Project description:A new class of water-soluble C60 transfecting agents has been prepared using Hirsch-Bingel chemistry and assessed for their ability to act as gene-delivery vectors in vitro. In an effort to elucidate the relationship between the hydrophobicity of the fullerene core, the hydrophilicity of the water-solubilizing groups, and the overall charge state of the C60 vectors in gene delivery and expression, several different C60 derivatives were synthesized to yield either positively charged, negatively charged, or neutral chemical functionalities under physiological conditions. These fullerene derivatives were then tested for their ability to transfect cells grown in culture with DNA carrying the green fluorescent protein (GFP) reporter gene. Statistically significant expression of GFP was observed for all forms of the C60 derivatives when used as DNA vectors and compared to the ability of naked DNA alone to transfect cells. However, efficient in vitro transfection was only achieved with the two positively charged C60 derivatives, namely, an octa-amino derivatized C60 and a dodeca-amino derivatized C60 vector. All C60 vectors showed an increase in toxicity in a dose-dependent manner. Increased levels of cellular toxicity were observed for positively charged C60 vectors relative to the negatively charged and neutral vectors. Structural analyses using dynamic light scattering and optical microscopy offered further insights into possible correlations between the various derivatized C60 compounds, the C60 vector/DNA complexes, their physical attributes (aggregation, charge) and their transfection efficiencies. Recently, similar Gd@C60-based compounds have demonstrated potential as advanced contrast agents for magnetic resonance imaging (MRI). Thus, the successful demonstration of intracellular DNA uptake, intracellular transport, and gene expression from DNA using C60 vectors suggests the possibility of developing analogous Gd@C60-based vectors to serve simultaneously as both therapeutic and diagnostic agents.

Dataset Information

Spin Signature of the C60 Fullerene Anion: A Combined X- and D-Band EPR and DFT Study.

Publications

Spin Signature of the C<sub>60</sub> Fullerene Anion: A Combined X- and D-Band EPR and DFT Study.

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