How the change of the ligand from L = porphine, P^{2∿/sup>, to L = P₄-substituted porphine, P(P)₄2∿/sup>, affects the electronic properties and the M-L binding energies for the first-ro}

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• 作者：Aleksey E. Kuznetsov ; ^{aleksey73kuznets@gmail.com" class="auth_mail" title="E-mail the corresponding author}
• 关键词：P4-substituted transition-metal-porphyrins ; Density functional theory ; Electronic properties ; NBO analysis ; Binding energies
• 刊名：Chemical Physics
• 出版年：2016
• 出版时间：1-13 May 2016
• 年：2016
• 卷：469-470
• 期：Complete
• 页码：38-48
• 全文大小：1552 K

文摘

We performed comparative DFT study, including Natural Bond Orbitals (NBO) analysis, of the binding energies between all the first-row transition metals Mⁿ⁺ (M = Sc–Zn) and two ligands of the similar type: porphine, P^2−, and its completely P-substituted counterpart, P(P)₄^2−. The main findings are as follows: (i) complete substitution of all the pyrrole nitrogens with P-atoms does not affect the ground spin state of metalloporphyrins; (ii) generally, for the MP(P)₄ compounds the calculated HOMO/LUMO gaps and optical gaps are smaller than for their MP counterparts; (iii) the trends in the change of the binding energies between Mⁿ⁺ and P(P)₄^2−/P^2− are very similar for both ligands. The complete substitution of the pyrrole nitrogens by the P-atoms decreases the Mⁿ⁺-ligand binding energies; all the MP(P)₄ compounds studied are stable according to the calculated E_bind values and therefore can be potentially synthesized.