Metal Complexes of 5,15‐Porphyrinquinones: Systematic Study of Crystal Structure, Electronic Structure, and Lewis Acidity

Yamashita, Ken‐ichi; Hirano, Daisuke; Sugiura, Ken‐ichi

doi:10.1002/ejic.202000527

Cited by 11 publications

(29 citation statements)

References 48 publications

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“…Reaction of the nickel complex, Ni‐ 1 , afforded an uncharacterized complex mixture. Considering an irreversible oxidation to Ni‐ 2 (0.96 V vs Fc/Fc + ), as revealed by cyclic voltammetry, once‐formed Ni‐ 2 might be decomposed under the reaction condition. Oxidation of free base 2 is also irreversible, although the potential is higher (1.18 V) than that of Ni‐ 2 .…”

Section: Resultsmentioning

confidence: 99%

“…Considering an irreversible oxidation to Ni‐ 2 (0.96 V vs Fc/Fc + ), as revealed by cyclic voltammetry, once‐formed Ni‐ 2 might be decomposed under the reaction condition. Oxidation of free base 2 is also irreversible, although the potential is higher (1.18 V) than that of Ni‐ 2 . Moreover, 2 would exist in protonated forms under the acidic reaction conditions, and protonation would increase its oxidation potential.…”

Section: Resultsmentioning

confidence: 99%

“…Metal complexes of 5,15‐PQs can be also be obtained similar to that of porphyrins . Very recently, we systematically studied the structure and physical properties of the divalent metal complexes of 5,15‐PQ . We revealed their unique characteristics such as effective d(metal)‐π(PQ) coupling in their molecular orbital and an enhanced Lewis acidity of the central metal.…”

Section: Introductionmentioning

confidence: 99%

“…By utilizing the reactivity of 5,15‐PQs, which is typical to that of quinones, further transformations of PQs were accomplished . Metal complexes of 5,15‐PQs can be also be obtained similar to that of porphyrins . Very recently, we systematically studied the structure and physical properties of the divalent metal complexes of 5,15‐PQ .…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Yamashita

Hirano

Fujimaki

et al. 2020

Chemistry An Asian Journal

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Treatment of a meso-diarylporphyrin with PhI(OAc) 2 in the presence of BF 3 • OEt 2 and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso-meso β-β doubly-fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000 nm. It has a low HOMO-LUMO gap owing to expanded and low-symmetry π-planes.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Yamashita

Hirano

Fujimaki

et al. 2020

Chemistry An Asian Journal

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“…In the equation for Ni II , the same molar extinction coefficient between 5-coordinate and 6-coordinate complexes was assumed as these complexes were similar to other Ni II -porphyrin analogs. [21,22,32] We also assumed that the synthesis of Ni II -1•(DABCO) in •(DABCO) out 2 from Ni II -1•(DABCO) in involved only one step with one equilibrium constant (K2).…”

Section: Determination Of Binding Constantsmentioning

confidence: 99%

Outstanding Enhancement in the Axial Coordination Ability of the Highly Rigid Cofacial Cyclic Metalloporphyrin Dimer

Yamashita

Furutani²,

Ogawa³

2021

Preprint

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<div>Copper- and nickel-porphyrin complexes show extremely weak axial coordination ability without any electron-withdrawing groups. Herein, we report axial ligation on CuII- and NiII-porphyrins in a highly rigid cofacial porphyrin dimer with a bidentate ligand, 1,4-diazabicyclo[2.2.2]octane (DABCO). To the best of our knowledge, this is the first report on the use of CuII- and NiII-porphyrins for coordination-induced guest binding of porphyrin-based host molecules without the help of other metal ions. The high rigidity of the dimer induces guest binding through the cooperative effect of weak axial ligation. The results showed that CuII- and ZnII-complexes bind one DABCO molecule inside their cavities, whereas the NiII-complex binds two additional DABCO molecules outside to form a stable 6-coordinate paramagnetic NiII-complexes. </div>

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Redox‐Mediated Single‐Molecule Transistor with A Subthreshold Swing Down To 120 mV Decade⁻¹

Li,

Xu,

Zou

et al. 2023

Adv Funct Materials

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The single‐molecule electronic devices offer the ultimate solution to miniaturize integrated circuits, and subthreshold swing (SS) is the key indicator of the power consumption for single‐molecule transistors but is still quite restricted. In this study, the redox‐mediated single‐molecule transistor with a SS down to 120 mV decade−1 in the faradaic potential region via the electrochemical‐STM break junction (EC‐STM‐BJ) technique is fabricated. With an off‐state leakage current of less than 10 pA and an on/off ratio of 100, the balance between low static power consumption and a high switching ratio is achieved. The theoretical investigations reveal that the conductance tuning is from the difference of transmission in the redox process. The study provides a new strategy for the design of single‐molecule transistors with promising SS, which is essential for the potential application of single‐molecule devices.

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Metal Complexes of 5,15‐Porphyrinquinones: Systematic Study of Crystal Structure, Electronic Structure, and Lewis Acidity

Abstract: We conducted the first systematic study on the synthesis, structure, and properties of various divalent metal complexes (Ni

Cited by 11 publications

References 48 publications

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Outstanding Enhancement in the Axial Coordination Ability of the Highly Rigid Cofacial Cyclic Metalloporphyrin Dimer

Redox‐Mediated Single‐Molecule Transistor with A Subthreshold Swing Down To 120 mV Decade⁻¹

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Metal Complexes of 5,15‐Porphyrinquinones: Systematic Study of Crystal Structure, Electronic Structure, and Lewis Acidity

Abstract: We conducted the first systematic study on the synthesis, structure, and properties of various divalent metal complexes (Ni

Cited by 11 publications

References 48 publications

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Synthesis of Porphyrinquinone and Doubly‐Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound

Outstanding Enhancement in the Axial Coordination Ability of the Highly Rigid Cofacial Cyclic Metalloporphyrin Dimer

Redox‐Mediated Single‐Molecule Transistor with A Subthreshold Swing Down To 120 mV Decade−1

Contact Info

Product

Resources

About

Redox‐Mediated Single‐Molecule Transistor with A Subthreshold Swing Down To 120 mV Decade⁻¹