Rethinking gold(II) porphyrins: an inherent wave distortion
Relativistic DFT (OLYP-D3/ZORA-STO-TZ2P) calculations predict low adiabatic ionization potentials for gold(II) porphyrins, from 4.60 eV for Au[TPP] (TPP $=$ tetraphenylporphyrin) to 5.34 eV for Au[TPFPP] [TPFPP $=$ tetrakis(pentafluorophenyl)porphyrin]. These values are over 1 eV lower than those ca...
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Académie des sciences
2024-01-01
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| Online Access: | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.264/ |
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| author | Ghosh, Abhik Conradie, Jeanet |
| author_facet | Ghosh, Abhik Conradie, Jeanet |
| author_sort | Ghosh, Abhik |
| collection | DOAJ |
| description | Relativistic DFT (OLYP-D3/ZORA-STO-TZ2P) calculations predict low adiabatic ionization potentials for gold(II) porphyrins, from 4.60 eV for Au[TPP] (TPP $=$ tetraphenylporphyrin) to 5.34 eV for Au[TPFPP] [TPFPP $=$ tetrakis(pentafluorophenyl)porphyrin]. These values are over 1 eV lower than those calculated for analogous silver(II) porphyrins, reflecting much greater relativistic destabilization of the Au 5d orbitals relative to Ag 4d orbitals. Interestingly, our calculations also place the observed structural distortion of Au[TPP] in an entirely new light. The electronic imperative of the Au(II) center to assume a pseudo-d10 configuration drives a wave deformation of the porphyrin core that allows for Au(d$_{x^{2}\mbox {-}y^{2}}$)–porphyrin(${\pi }$) mixing. The lateral compression–elongation of the porphyrin (unequal pairs of Au–N bonds), in contrast, appears to be a secondary effect, a consequence of the wave deformation. The wave distortion results in significant ${\pi }$ spin populations on the porphyrin macrocycle, leaving behind only about 20–25% of the spin density on the gold. The effect is specific to gold: silver(II) porphyrins exhibit strictly planar cores with approximate $D_{4\mathrm{h}}$ local symmetry at the metal. |
| format | Article |
| id | doaj-art-c70eede265da4d63a887b16ec218eeb1 |
| institution | Kabale University |
| issn | 1878-1543 |
| language | English |
| publishDate | 2024-01-01 |
| publisher | Académie des sciences |
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| spelling | doaj-art-c70eede265da4d63a887b16ec218eeb12025-02-07T13:39:09ZengAcadémie des sciencesComptes Rendus. Chimie1878-15432024-01-0127S110511210.5802/crchim.26410.5802/crchim.264Rethinking gold(II) porphyrins: an inherent wave distortionGhosh, Abhik0https://orcid.org/0000-0003-1161-6364Conradie, Jeanet1https://orcid.org/0000-0002-8120-6830Department of Chemistry, University of Tromsø, N-9037 Tromsø, NorwayDepartment of Chemistry, University of Tromsø, N-9037 Tromsø, Norway; Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein 9300, Republic of South AfricaRelativistic DFT (OLYP-D3/ZORA-STO-TZ2P) calculations predict low adiabatic ionization potentials for gold(II) porphyrins, from 4.60 eV for Au[TPP] (TPP $=$ tetraphenylporphyrin) to 5.34 eV for Au[TPFPP] [TPFPP $=$ tetrakis(pentafluorophenyl)porphyrin]. These values are over 1 eV lower than those calculated for analogous silver(II) porphyrins, reflecting much greater relativistic destabilization of the Au 5d orbitals relative to Ag 4d orbitals. Interestingly, our calculations also place the observed structural distortion of Au[TPP] in an entirely new light. The electronic imperative of the Au(II) center to assume a pseudo-d10 configuration drives a wave deformation of the porphyrin core that allows for Au(d$_{x^{2}\mbox {-}y^{2}}$)–porphyrin(${\pi }$) mixing. The lateral compression–elongation of the porphyrin (unequal pairs of Au–N bonds), in contrast, appears to be a secondary effect, a consequence of the wave deformation. The wave distortion results in significant ${\pi }$ spin populations on the porphyrin macrocycle, leaving behind only about 20–25% of the spin density on the gold. The effect is specific to gold: silver(II) porphyrins exhibit strictly planar cores with approximate $D_{4\mathrm{h}}$ local symmetry at the metal.https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.264/GoldPorphyrinNonplanar distortionLigand noninnocenceRelativistic effect |
| spellingShingle | Ghosh, Abhik Conradie, Jeanet Rethinking gold(II) porphyrins: an inherent wave distortion Comptes Rendus. Chimie Gold Porphyrin Nonplanar distortion Ligand noninnocence Relativistic effect |
| title | Rethinking gold(II) porphyrins: an inherent wave distortion |
| title_full | Rethinking gold(II) porphyrins: an inherent wave distortion |
| title_fullStr | Rethinking gold(II) porphyrins: an inherent wave distortion |
| title_full_unstemmed | Rethinking gold(II) porphyrins: an inherent wave distortion |
| title_short | Rethinking gold(II) porphyrins: an inherent wave distortion |
| title_sort | rethinking gold ii porphyrins an inherent wave distortion |
| topic | Gold Porphyrin Nonplanar distortion Ligand noninnocence Relativistic effect |
| url | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.264/ |
| work_keys_str_mv | AT ghoshabhik rethinkinggoldiiporphyrinsaninherentwavedistortion AT conradiejeanet rethinkinggoldiiporphyrinsaninherentwavedistortion |