caa a22 4500 605510741 CHVBK 20210128100647.0 cr unu---uuuuu 210128e20150101xx s 000 0 eng 10.1007/s00894-015-2570-z doi (NATIONALLICENCE)springer-10.1007/s00894-015-2570-z Charge transfer complexes of fullerene[60] with porphyrins as molecular rectifiers. A theoretical study [Elektronische Daten] [Filiberto Montiel, Lioudmila Fomina, Serguei Fomine] 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. Springer-Verlag Berlin Heidelberg, 2015 DFT nationallicence Fullerene nationallicence Molecular diode nationallicence Porphyrin nationallicence Rectification nationallicence Montiel Filiberto Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, 04510, Coyoacán, Mexico DF, Mexico aut Fomina Lioudmila Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, 04510, Coyoacán, Mexico DF, Mexico aut Fomine Serguei Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, 04510, Coyoacán, Mexico DF, Mexico aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/1(2015-01-01), 1-8 1610-2940 21:1<1 2015 21 894 https://doi.org/10.1007/s00894-015-2570-z text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2570-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Montiel Filiberto Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, 04510, Coyoacán, Mexico DF, Mexico aut NATIONALLICENCE 700 1- Fomina Lioudmila Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, 04510, Coyoacán, Mexico DF, Mexico aut NATIONALLICENCE 700 1- Fomine Serguei Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, 04510, Coyoacán, Mexico DF, Mexico aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/1(2015-01-01), 1-8 1610-2940 21:1<1 2015 21 894