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Metal-free and transition-metal tetraferrocenylporphyrins part 1: synthesis, characterization, electronic structure, and conformational flexibility of neutral compounds

Nemykin, Victor N. and Galloni, Pierluca and Floris, Barbara and Barrett, Christopher D. and Hadt, Ryan G. and Subbotin, Roman I. and Marrani, Andrea G. and Zanoni, Robertino and Loim, Nikolay M. (2008) Metal-free and transition-metal tetraferrocenylporphyrins part 1: synthesis, characterization, electronic structure, and conformational flexibility of neutral compounds. Dalton Transactions, 2008 (32). pp. 4233-4246. ISSN 1477-9226. doi:10.1039/b805156a.

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H_2TFcP [TFcP = 5,10,15,20-tetraferrocenyl porphyrin(2-)] was prepared by a direct tetramerization reaction between pyrrole and ferrocene carbaldehyde in the presence of a BF_3 catalyst, while the series of MTFcP (M = Zn, Ni, Co and Cu) were prepared by a metallation reaction between H_2TFcP and respective metal acetates. All compounds were characterized by UV-vis and MCD spectroscopy, APCI MS and MS/MS methods, high-resolution ESI MS and XPS spectroscopy. Diamagnetic compounds were additionally characterized using ^1H and ^(13)C NMR methods, while the presence of low-spin iron(ii) centers in the neutral compounds was confirmed by Mössbauer spectroscopy and by analysis of the XPS Fe 2p peaks, revealing equivalent Fe sites. XPS additionally showed the influence on Fe 2p binding energies exerted by the distinct central metal ions. The conformational flexibility of ferrocene substituents in H_2TFcP and MTFcP, was confirmed using variable-temperature NMR and computational methods. Density functional theory predicts that α,β,α,β atropisomers with ruffled porphyrin cores represent minima on the potential energy surfaces of both H_2TFcP and MTFcP. The degree of non-planarity is central-metal dependent and follows the trend: ZnTFcP < H_2TFcP approximately CuTFcP < CoTFcP < NiTFcP. In all cases, a set of occupied, predominantly ferrocene-based molecular orbitals were found between the highest occupied and the lowest unoccupied, predominantly porphyrin-based molecular orbitals. The vertical excitation energies of H_2TFcP were calculated at the TDDFT level and confirm the presence of numerous predominantly metal-to-ligand charge-transfer bands coupled via configurational interaction with expected intra-ligand π-π* transitions.

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Hadt, Ryan G.0000-0001-6026-1358
Additional Information:© The Royal Society of Chemistry 2008. Received 26th March 2008, Accepted 30th May 2008. First published on 9th July 2008. Generous support from the NSF (CHE-0809203) Research Corporation (Cottrell College Science Award CC6766), University of Minnesota Grant-in-Aid (Grant 20209) and Minnesota Supercomputing Institute to VN as well as University of Minnesota Duluth Undergraduate Research Opportunity Grants to RH and CB is greatly appreciated. We also wish to thank Dr N. Kobayashi for the possibility to collect preliminary MCD data on H2TFcP and ZnTFcP, Dr E. Polshin for help with Mössbauer experiments, Dr R. Belosludov for help with TDDFT calculations, Dr A. Oyler for help with APCI spectra and Dr A. Koposov for help with NMR spectroscopy.
Funding AgencyGrant Number
Cottrell Scholar of Research CorporationCC6766
University of Minnesota Duluth20209
Minnesota Supercomputing InstituteUNSPECIFIED
Issue or Number:32
Record Number:CaltechAUTHORS:20180612-161521832
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87040
Deposited By: George Porter
Deposited On:12 Jun 2018 23:22
Last Modified:15 Nov 2021 20:44

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