Quantum chemical studies of the electronic structures of anti-tumor agents: AuIIIL+ (L = porphine, tetraphenylporphyrin)

Fu, Wenjie; Li, Wan‐Lu; Zhang, Yixiang; Zhang, Jingxuan; Li, Jun

doi:10.1016/j.comptc.2022.113685

Cited by 1 publication

(3 citation statements)

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“…The average distance between the four S atoms and the porphyrin ring plane in the porphyrin ligand was 4.3 Å for H 2 P and 4.1 Å for AuP + (Figure S8), which are longer than that of 5,10,15,20-tetrakis(α,α,α,α- o -acetylthiomethylphenyl)porphyrin (3.4 Å) and shorter than that of 5,10,15,20-tetrakis(α,α,α,α- o -acetylthioethylphenyl)porphyrin (4.9 Å) . The HOMO/LUMO energy levels of H 2 P and AuP + were calculated to be −5.35/–2.61 eV and −8.04/–5.23 eV, respectively, which are comparable with previously reported values for the free-base tetraphenylporphyrin (H 2 TPP) and its Au III complex ([Au III TPP] + ). , …”

Section: Methodsmentioning

confidence: 99%

“…20 The HOMO/LUMO energy levels of H 2 P and AuP + were calculated to be −5.35/−2.61 eV and −8.04/−5.23 eV, respectively, which are comparable with previously reported values for the free-base tetraphenylporphyrin (H 2 TPP) 24 and its Au III complex ([Au III TPP] + ). 22,25 Synthesis of the Porphyrin-Protected AuCs. An aqueous solution (Milli-Q, 2 mL) of HAuCl 4 •4H 2 O (2.06 mg, 5.00 μmol) and a CH 2 Cl 2 solution (500 μL) of tetraoctylammonium chloride (TOACl, 3.14 mg, 6.25 μmol) were mixed in a 5 mL vial.…”

Section: T H Imentioning

confidence: 99%

“…We synthesized 1.3 nm diameter AuCs protected by a free-base porphyrin with thioacetylacetoamide moieties (H 2 P) to ensure a long distance between the porphyrin ring and AuC. We also designed a Au III complex of H 2 P (AuP + ) that has a lower-energy highest occupied molecular orbital (HOMO) 22,25 than H 2 P. The time-resolved photodynamics of these porphyrin-protected AuCs were elucidated by femtosecond transient absorption (TA) measurements, which revealed that AuC acts as an electron acceptor from H 2 P, whereas AuC acts as an electron donor to AuP + (Scheme 1). The electron-transfer direction between the AuC and porphyrin ligand can be easily controlled by the central metal ion of the protecting ligand.…”

Section: ■ Introductionmentioning

confidence: 99%

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Tuning the Direction of Photoinduced Electron Transfer in Porphyrin-Protected Gold Clusters

Chiga,

Suzuki,

Takahata

et al. 2024

J. Phys. Chem. C

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The interfacial electron-transfer reaction in ligand-protected gold clusters (AuCs) has been extensively investigated, but there are limited reports on organic chromophore ligands for photoinduced electron-transfer reactions of chromophoreattached AuCs. Here, we focused on porphyrins as chromophore ligands because of their tunable redox properties through the insertion of metal ions. We synthesized 1.3 nm diameter AuCs face-coordinated by free-base porphyrin (H 2 P) or Au III porphyrin (AuP + ) as photofunctional ligands. The synthesized H 2 P-and AuP + -protected AuCs (H 2 P-AuCs and AuP + -AuCs) were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and ultraviolet−visible−near-infrared absorption spectroscopy. Femtosecond transient absorption measurements revealed the photodynamics of H 2 P-AuCs and AuP + -AuCs. The AuCs in H 2 P-AuCs and AuP + -AuCs act as electron acceptors and electron donors, respectively, achieving control of the photoinduced electron-transfer direction by inserting the metal ion into the porphyrin ligand. This drastic change is caused by the high electrophilicity of AuP + , indicating that the precise design of the protecting ligand can expand the potential of AuCs as photofunctional materials.

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