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Charge transfer complexes of fullerene[60] with porphyrins as molecular rectifiers. A theoretical study

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Abstract

Molecular diodes based on charge transfer complexes of fullerene[60] with different metalloporphyrins have been modeled. Their current–voltage characteristics and the rectification ratios (RR) were calculated using direct ab initio method at PBE/def2-SVP level of theory with D3 dispersion correction, for voltages ranging from −2 to +2 V. The highest RR of 32.5 was determined for the complex of fullerene[60] with zinc tetraphenylporphyrin at 0.8 V. Other molecular diodes possessed lower RR, however, all complexes showed RR higher than 1 at all bias voltages. The asymmetric evolutions and alignment of the molecular orbitals with the applied bias were found to be essential for generating the molecular diode rectification behavior. Metal nature of metalloporphyrins and the interaction porphyrin–electrode significantly affect RR of molecular diode. Large metal ions like Cd2+ and Ag2+ in metalloporphyrins disfavor rectification creating conducting channels in two directions, while smaller ions Zn2+ and Cu2+ favor rectification increasing the interaction between gold electrode and porphyrin macrocycle.

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Acknowledgments

This research was carried out with the support of Grant 151277 from National Council for Science and Technology (CONACyT), we also would like to thank General Direction of Computing and Information Technologies and Communication of the National Autonomous University of Mexico (DGTIC-UNAM) for use of supercomputer facilities.

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  1. Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, Mexico DF, 04510, Mexico

    Filiberto Montiel, Lioudmila Fomina & Serguei Fomine

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  1. Filiberto Montiel
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  2. Lioudmila Fomina
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  3. Serguei Fomine
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Correspondence to Serguei Fomine.

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Montiel, F., Fomina, L. & Fomine, S. Charge transfer complexes of fullerene[60] with porphyrins as molecular rectifiers. A theoretical study. J Mol Model 21, 4 (2015). https://doi.org/10.1007/s00894-015-2570-z

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