Evolution of electronic and vibronic transitions in metal(II) meso-tetra(4-pyridyl)porphyrins

Lopes, J.M.S.; Sampaio, Renato N.; Ito, Amando Siuiti; Batista, A.A.; Machado, Antônio Eduardo da Hora; Araújo, Paulo T.; Neto, N.M. Barbosa

doi:10.1016/j.saa.2019.02.024

Cited by 24 publications

(14 citation statements)

References 34 publications

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“…36 Additionally, there is no evidence of the N−H stretch associated with the starting oxamide ligand. Comparison of the Co prism to its Zn-analogue reveals near identical IR signatures, further 43,44 Examining the Q-bands, the Zn prisms exhibit two distinct, well-resolved Q-bands, while the Co prisms seem to show a single Q-band (Supporting Information). This agrees with other cobalt porphyrins in the literature and suggests the geometry at the metal center is near ideal D 4h point symmetry for cobalt-containing prisms and more distorted from square planar for the Zn prisms.…”

Section: ■ Results and Discussionmentioning

confidence: 89%

“…Electronic absorption spectroscopy reveals the expected Soret band and Q-bands, indicative of a metalated porphyrin. The Co prism Soret bands appeared around 415–420 nm, consistent with other Co(II)-porphyrin complexes in the literature (Co(III) porphyrins typical display Soret bands at ∼435–450 nm). , Examining the Q-bands, the Zn prisms exhibit two distinct, well-resolved Q-bands, while the Co prisms seem to show a single Q-band (Supporting Information). This agrees with other cobalt porphyrins in the literature and suggests the geometry at the metal center is near ideal D 4 h point symmetry for cobalt-containing prisms and more distorted from square planar for the Zn prisms …”

Section: Resultsmentioning

confidence: 99%

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Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks

et al. 2020

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We assembled eight cofacial porphyrin prisms using MTPyP (M = Co(II) or Zn(II), TPyP = 4-tetrapyridylporphyrin) and functionalized ruthenium-based “molecular clips” using coordination-driven self-assembly. Our approach allows for the rapid synthesis of these architectures in isolated yields as high as 98% for the assembly step. Structural and reactivity studies provided a deeper understanding of the role of the building blocks on the oxygen reduction reaction (ORR). Catalytic efficacy was probed by using cyclic and hydrodynamic voltammetry on heterogeneous catalyst inks in aqueous media. The reported prisms showed outstanding selectivity (>98%) for the kinetically hindered 4e–/4H+ reduction of O2 to H2O over the kinetically more accessible 2e–/2H+ reduction to H2O2. Furthermore, we have demonstrated significant cofacial enhancement in the observed catalytic rate constant k s (∼5 orders of magnitude) over the mononuclear analogue. We conclude that the steric bulk of the clip plays an important role in the structural dynamics of these prisms, which in turn modulates the ORR reactivity with respect to selectivity and kinetics.

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Section: ■ Results and Discussionmentioning

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks

et al. 2020

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“…These compounds were synthesized by referring to the literature. 21 The supramolecular organization in the vapordeposited MTPyP film was investigated by using the twodimensional grazing incidence X-ray diffraction (2D-GIXD) and infrared p-polarized multiple-angle incidence resolution spectrometry (IR pMAIRS) 22 techniques (detailed experimental conditions are in the ESI †).…”

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confidence: 99%

Control of supramolecular organizations by coordination bonding in tetrapyridylporphyrin thin films

et al. 2022

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“…These emission bands have been assigned to Qx(0-0) and Qx(0-1) transitions. This is characteristic of porphyrins with D2h symmetry, indicating that the vibronic structure of the tetrapyrrolic macrocycle remains practically unchanged upon excitation [9]. The emission spectrum of ZnTEPP is characterized by a broad emission band centered at 620 nm and a second band at 680 nm.…”

Section: Photophysical Characterizationmentioning

confidence: 93%

Synthesis of Conjugated Polymer Based in Zn(II) Porphyrin Bearing Terminal Alkynyl Groups as Photosensitizer

Santamarina

Heredia

Durantini

et al. 2020

The 24th International Electronic Conference on Synthetic Organic Chemistry

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5,10,15,20-tetrakis-[4-(ethynyl)phenyl]porphyrin (TEP) was synthesized from the condensation of 4-(ethynyl)benzaldehyde and pyrrole catalyzed by boron trifluoride diethyl etherate in dichloromethane (DCM). After oxidation with 2,3-dichloro-5,6-dicyano-1,4benzoquinone and purification, TEP was obtained in 34% yield. This porphyrin was metaled with Zn(II) acetate in DCM/methanol to produce the complex ZnTEP in 98% yield. Homocoupling reaction of terminal alkynes of ZnTEP to diynes was used to synthesize conjugated polymer organogel (ZnTEPP). The reaction was cocatalyzed by PdCl2(PPh3)2 and CuI in tetrahydrofuran. The solvent was evaporated to obtain xerogel and the SEM images showed microporous structure. In addition, spectroscopic and photodynamic studies of ZnTEPP indicated that the porphyrin unit retains its properties as a photosensitizer. Thus, this polymer is an interesting material with potential applications to form photoactive aseptic surfaces.

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Evolution of electronic and vibronic transitions in metal(II) meso-tetra(4-pyridyl)porphyrins

Cited by 24 publications

References 34 publications

Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks

Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks

Control of supramolecular organizations by coordination bonding in tetrapyridylporphyrin thin films

Synthesis of Conjugated Polymer Based in Zn(II) Porphyrin Bearing Terminal Alkynyl Groups as Photosensitizer

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