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. 2020 Jan 2;10(1):533-540.
doi: 10.1039/c9ra09228e. eCollection 2019 Dec 20.

Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal-ligand interactions

Kolle E Thomas  1 , Nicolas Desbois  2 , Jeanet Conradie  1   3 , Simon J Teat  4 , Claude P Gros  2 , Abhik Ghosh  1
Affiliations

Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal-ligand interactions

Kolle E Thomas et al. RSC Adv. .

Abstract

Given that noninnocent and metalloradical-type electronic structures are ubiquitous among dipyrrin-bisphenolate (DPP) complexes, we synthesized the gold(iii) derivatives as potentially innocent paradigms against which the properties of other metallo-DPP derivatives can be evaluated. Electronic absorption spectra, electrochemical studies, a single-crystal X-ray structure, and DFT calculations all suggest that the ground states of the new complexes indeed correspond to an innocent AuIII-DPP3-, paralleling a similar description noted for Au corroles. Interestingly, while DFT calculations indicate purely ligand-centered oxidations, reduction of AuDPP is predicted to occur across both the metal and the ligand.

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Conflict of interest statement

There are no conflicts of interest to declare.

Figures

Fig. 1
Fig. 1. Free-base dipyrrin-bisphenol and meso-triarylcorrole ligands.
Fig. 2
Fig. 2. Molecular structure of Au[CF3DPP]: top view (above) with selected distances (Å) and side view (below).
Fig. 3
Fig. 3. UV-vis spectra of Au[XDPP] (X = CF3, H, and CH3) in dichloromethane.
Fig. 4
Fig. 4. UV-vis spectra of M[CF3DPP] (M = Cu and Au) in dichloromethane.
Fig. 5
Fig. 5. Cyclic voltammograms of Au[XDPP] (X = CF3, H and CH3) in benzonitrile. Scan rate: 0.1 V s−1.
Fig. 6
Fig. 6. Cyclic voltammograms of M[CF3DPP] (M = Cu and Au) in benzonitrile. Scan rate: for Cu is 0.05 V s−1 and 0.1 V s−1 for Au.
Fig. 7
Fig. 7. Juxtaposition of the OLYP/STO-TZ2P optimized geometries (Å) Cu (left) and Au (right) DPP complexes.
Fig. 8
Fig. 8. OLYP/STO-TZ2P frontier MOs of Au[DPP] under a C2v symmetry constraint.
Fig. 9
Fig. 9. OLYP/STO-TZ2P spin density and HOMO profiles of the cationic and anionic states of Au[DPP] optimized with a C2 symmetry constraint.
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