Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles

Yadav, Inderpal; Sankar, Muniappan

doi:10.1021/acs.inorgchem.3c02666

Cited by 4 publications

(3 citation statements)

References 92 publications

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“…b The MOs are visually depicted in Figure 6. formyl-, 45 dicyanovinyl-and dicyanobutadienyl-metallocorroles 46,47 in which strong NIR absorptions primarily reflect an extension of the corrole's conjugation, with varying contributions of corrole-to-substituent charge transfer character.…”

Section: ■ Resultsmentioning

confidence: 99%

“…Such transitions reflect a clean LUMO switch in these systems (relative to other meso -triarylcorroles and tetraarylporphyrins), from macrocycle- to meso -aryl-based, as a result of the relatively weak electronic coupling between the macrocycle and the significantly twisted (i.e., out-of-plane) aryl substituents. These systems may be contrasted with β-formyl-, dicyanovinyl- and dicyanobutadienyl- metallocorroles , in which strong NIR absorptions primarily reflect an extension of the corrole’s conjugation, with varying contributions of corrole-to-substituent charge transfer character.…”

Section: Discussionmentioning

confidence: 99%

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Inverse Hypercorroles

Osterloh,

Desbois,

Conradie

et al. 2024

Inorg. Chem.

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Ground-state and time-dependent density functional theory (TDDFT) calculations with the long-range-corrected, Coulomb-attenuating CAMY-B3LYP exchange-correlation functional and large, all-electron STO-TZ2P basis sets have been used to examine the potential "inverse hypercorrole" character of mesop-nitrophenyl-appended dicyanidocobalt(III) corrole dianions. The effect is most dramatic for 5,15-bis(p-nitrophenyl) derivatives, where it manifests itself in intense NIR absorptions. The 10-aryl groups in these complexes play a modulatory role, as evinced by experimental UV−visible spectroscopic and electrochemical data for a series of 5,15-bis(p-nitrophenyl) dicyanidocobalt(III) corroles. TDDFT (CAMY-B3LYP) calculations ascribe these features clearly to a transition from the corrole's a 2u -like HOMO (retaining the D 4h irrep used for metalloporphyrins) to a nitrophenyl-based LUMO. The outward nature of this transition contrasts with the usual phenyl-to-macrocycle direction of charge transfer transitions in many hyperporphyrins and hypercorroles; thus, the complexes studied are aptly described as inverse hypercorroles.

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Section: ■ Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Inverse Hypercorroles

Osterloh,

Desbois,

Conradie

et al. 2024

Inorg. Chem.

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“…These results show the increased conjugation at β-position(s) strongly redshifts absorption spectra and enhances the molar absorptivity of the Q-band. 12 The mass spectrometric analysis of investigated cobalt corroles is described in Fig. S2–S5 in the ESI †…”

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confidence: 99%

Structurally influenced optical nonlinearities and ultrafast dynamics in β-acroleyl- and β-dicyanobutadienyl-appended cobalt corroles

Yadav,

Acharyya,

Prakash

et al. 2024

Phys. Chem. Chem. Phys.

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Synthesis and Understanding of the Role of Donor-Tetracyanobutadiene in Porphyrin β-Periphery toward Ultrafast Charge Transfer Dynamics

Dawson,

Sekaran,

Das

et al. 2024

J. Phys. Chem. C

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The porphyrins, structurally analogous to chlorophyll pigment, have drawn significant interest in mimicking natural photosynthetic processes in energy conversion applications. In this work, a new set of β-substituted freebase (H 2 P) and zinc-porphyrins (ZnP) have been designed (5−19) and synthesized employing ferrocene (Fc), triphenylamine (TPA), and carbazole (Cz) as secondary donors (D) and further incorporated tetracyanobuta-1,3diene (TCBD) as strong electron acceptor (A) entity following Sonogashira cross-coupling and subsequent [2 + 2] cycloaddition−retroelectrocyclization reactions. Steady-state optical data exhibit a broad absorption in the 650−800 nm region, particularly in 15−19, corroborating ground-state charge polarization leading to intramolecular charge transfer (CT) in these systems. Strong fluorescence quenching in all of the systems (5−19) compared to the control compounds (C1 and C2) further suggests excited-state nonradiative photoprocesses predominate in these β-substituted dyads and triads, particularly after TCBD incorporations (15−19). Though the secondary donors quickly oxidize in 5−10, the same becomes difficult in 15−19, indicating an electronic influence of TCBD, leading to the respective formation of MP •− -D •+ and MP •+ -A •− -D (MP = 2H or Zn) charge-separated (CS) species in a polar environment, which the molecular orbital positioning of the CT entities from computational studies has also justified. Finally, spectral and temporal dynamics of different photoproducts in these compounds have been assessed from femtosecond transient absorption studies, and subsequent fitting of the transient data identifies Cz contributing to the most stable and thus long-lived CS states, brightening their outstanding promise in solar energy harvesting and related electronic applications.

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Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles

Cited by 4 publications

References 92 publications

Inverse Hypercorroles

Inverse Hypercorroles

Structurally influenced optical nonlinearities and ultrafast dynamics in β-acroleyl- and β-dicyanobutadienyl-appended cobalt corroles

Synthesis and Understanding of the Role of Donor-Tetracyanobutadiene in Porphyrin β-Periphery toward Ultrafast Charge Transfer Dynamics

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