Prolonged Exciton Lifetime Is Achieved in Porphyrin Nanoring by Template Engineering: A Nonadiabatic Tight Binding Approach

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Prolonged Exciton Lifetime Is Achieved in Porphyrin Nanoring by Template Engineering: A Nonadiabatic Tight Binding Approach

The Journal of Physical Chemistry Letters. 2024. Vol. 15. No. 17. P. 4737–4744.

Mondal S., Habib M., Sarkar R., Pal S.

Porphyrin nanoring has been attracting immense attention due to its light harvesting capacity and potential applications in optical, catalysis, sensor, and electronic devices. We demonstrate by nonadiabatic quantum dynamics simulations that the photovoltaic efficiency can be enhanced by template engineering. Altering the hexadentate template (T6) with two tridentate templates (2T3) within the porphyrin ring (P6) cavity accelerated the electron transfer twice and suppressed the electron–hole recombination by nearly three times. The atomistic tight-binding simulation rationalized the dynamics by different localizations of charge of the band edge states, changes in nonadiabatic coupling, alteration in quantum coherence, and involvement of diverse electron–phonon vibrational modes. Further 2T3 templates more strongly hold the P6 ring than T6, reducing the structural fluctuation. As a result, the nonadiabatic coupling becomes weaker and suppresses the carrier recombination. Current atomistic simulation presents a template engineering strategy to enhance the exciton lifetime along with ultrafast charge separation, crucial factors for photovoltaic applications.

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1D and 2D coordination polymers based on ring-reduced free-base and copper-containing meso-tetra(4-pyridyl)porphyrins and MIII(TMHD)3 units (M = Dy, Tb and Gd; TMHD: 2,2,6,6-tetramethyl-3,5-heptanedionate)

Nazarov D., Yakushev I. A., Aleksey V. Kuzmin et al., Inorganic Chemistry Frontiers 2026 Vol. 13 No. 11 P. 5039–5050

Reduced tetra(4-pyridyl)porphyrins (H 2 TPyP and Cu II TPyP) form polymers with M III (TMHD) 3 (M = Dy, Tb and Gd). Folded zigzag 2D and linear 1D polymers are obtained. Their structure, optical and magnetic properties are investigated. ...

Added: September 14, 2026

Binuclear Coordination Assemblies of Metal Tetraphenylporphyrins (M = Mn, Fe, and In) with Anionic Thioindigo Bridges as Promising Magnetic Systems with Tunable Properties

Nazarov D., Maxim A. Faraonov, Nations S. et al., Inorganic Chemistry 2024 Vol. 63 No. 48 P. 22677–22687

A series of hybrids comprising two metal (Mn, Fe, and In) tetraphenylporphyrins axially substituted with anionic bidentate trans-thioindigo ligands (TI) were obtained. Substitution of the axial chloride anion by an oxygen atom of the dye forms short M–O bonds. Crystalline binuclear assemblies (TI•–)·{[MnIITPP]0·[MnIIITPP]+}·xC6H4Cl2 (x = 2 for 1 or 1 for 2) and (TI2–){[MIIITPP]+}2·xC6H4Cl2 (M ...

Added: September 14, 2026

Expanded Porphyrin exhibiting offcentered out-of-plane coordination to Dysprosium

Nazarov D., Labella J., Alexey V. Kuzmin et al., CCS CHEMISTRY 2024 Vol. 6 No. 7 P. 1731–1738

The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets. In this context, the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control. Herein, taking inspiration from on-surface chemistry, we explored the coordination of Dy3+ to a six-membered porphyrinoid, namely, the hemihexaphyrazine ...

Added: September 14, 2026

Tuning the magnetic coupling between manganese porphyrins in the 2MnIITPP⋅L assemblies, where L is 6,13-pentacenequinone, isoviolanthrone2− and {MnII(triazole−)2Pc}2−. Key role of a linker (L) in magnetic exchange

Nazarov D., Faraonov M., Kuzmin A. V. et al., Dyes and Pigments 2024 Vol. 223 P. 111926

Coordination architectures involving high-spin S = 5/2 manganese (II) tetraphenylporphyrins (MnIITPP) and a series of π-conjugated linkers have been obtained. Different molecules (isoviolanthrone, 6,13-pentacenequinone, 1,2,4-triazole anions coordinated to manganese (II) phthalocyanine [(MnII(triazole−)2Pc)]2−) in either dianion or neutral states were used as linkers in these architectures. Complexes [cryptand(K+)]2⋅[(isoviolanthrone2−)⋅{MnIITPP}2]2−⋅5C6H4Cl2 (1) and [(6,13-pentacenequinone0)⋅{MnIITPP}2]0⋅2C6H4Cl2 (2) are formed as a ...

Added: September 14, 2026

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Dey S., Mondal S., Chowdhury U. et al., The Journal of Physical Chemistry Letters 2026 Vol. 148 No. 36 P. 38820–38828

To forecast more active photovoltaic materials, the recent effort has concentrated on the charge transfer dynamics in host–guest systems. Charge carrier dynamics of buckybowl-substituted phenanthrenes in azabuckybowl@C60 hybrids have been investigated employing nonadiabatic molecular dynamics within the density-based tight-binding framework. Our investigation shows 3,6-azabuckybowl@C60 exhibits quicker electron transfer of 803 fs, well corroborated with experiment. Whereas 2,7-azabuckybowl@C60 produces ...

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Chowdhury U., Mondal S., Dey S. et al., Journal of the american chemical society 2026 Vol. 148 No. 23 P. 24538–24550

Covalent functionalization offers a versatile platform to engineer carbon nanotube properties for optoelectronics applications. We demonstrate by atomistic quantum dynamics simulation that covalent functionalization can renormalize the CNT band gap, split the degenerate CNT band edge states, and strongly influence charge carrier separation and recombination dynamics. Open-ring CNT functionalization (O-CNT) largely retains the π-conjugation, whereas ...

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Uskov F., Korobkov S., Birin K. P. et al., Journal of Photochemistry and Photobiology A: Chemistry 2026 Vol. 474 Article 116936

Oxidation of sulfides by singlet oxygen has been extensively studied, yet the structure-photoactivity relationship of these photosensitizers remains underinvestigated. In the present work the photocatalytic performance of a set of functionalized palladium(II) porphyrinates was comprehensively investigated in the photocatalytic oxidation of sulfides to reveal mutual influence of structural peculiarities onto the photosensitizing properties. The photophysical ...

Added: May 27, 2026

Quantum Simulation of Carrier Dynamics in Nanographene-fused Carbaporphyrin Tweezers@C60 Heterojunctions: Role of Dihedral Angle Engineering

Chowdhury U., Sarkar R., Sarkar P. et al., Nanoscale 2026 No. 15 P. 8115–8126

Added: April 1, 2026

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Sarkar R., Habib M., Pal S. et al., Nanoscale 2018 Vol. 10 No. 26 P. 12683–12694

The versatile photochemical properties of porphyrin molecules make them excellent candidates for solar energy applications. Carbon nanotubes (CNTs) exhibit superior charge conductivity and have been combined with porphyrins to achieve efficient and ultrafast charge separation. Experiments show that the charge separated state lives less than 10 ps, which is too short for applications. Using real-time ...

Added: November 19, 2025

Controlling the Charge Transfer and Recombination Dynamics in Hollow ZnO QD Based Dye Sensitized Solar Cell: An Insight from Ab Initio Simulation

Habib M., Ghosh N. N., Sarkar R. et al., Chemical Physics Letters 2018 Vol. 709 P. 21–25

First principle calculations are performed to study the charge transfer and recombination dynamics at the interface of dye-(ZnO)n hollow quantum dot (QD). It has been revealed that the extent of dye-ZnO interaction depends on the size of the QD which severely affects the driving force for charge transfer and recombination. The deep level conduction band of a particular ...

Added: November 19, 2025

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Sarkar R., Habib M., Kar M. et al., Nanoscale Advances 2020 Vol. 2 No. 4 P. 1502–1511

Nonradiative electron–hole (e–h) recombination is the primary source of energy loss in photovoltaic cells and inevitably, it competes with the charge transfer process, leading to poor device performance. Therefore, much attention has to be paid for delaying such processes; increasing the excitonic lifetime may be a solution for this. Using the real-time, density functional tight-binding ...

Added: November 19, 2025

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Sarkar R., Habib M., Pal S. et al., Journal of Applied Physics 2021 Vol. 129 No. 2 P. 025501

Supramolecular nanohybrids composed of carbon nanotubes (CNTs) and organic molecules are appealing candidates for many applications. We investigate charge separation and recombination dynamics in extended tetrathiafulvalene (exTTF), a well-known sulfur (S)-rich electron donor, immobilized on a CNT surface, and study the role of the chalcogen atom by comparing with the selenium (Se)-rich tetraselenafulvalene (exTSeF) analog. ...

Added: November 19, 2025

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Sarkar R., Kar M., Habib M. et al., Journal of the american chemical society 2021 Vol. 143 No. 17 P. 6649–6656

Carbon nanotubes (CNTs) are appealing candidates for solar and optoelectronic applications. Traditionally used as electron sinks, CNTs can also perform as electron donors, as exemplified by coupling with perylenediimide (PDI). To achieve high efficiencies, electron transfer (ET) should be fast, while subsequent charge recombination should be slow. Typically, defects are considered detrimental to material performance ...

Added: November 19, 2025

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Sarkar R., Habib M., Kovalenko S. M. et al., Journal of Physical Chemistry C 2021 Vol. 125 No. 30 P. 16620–16628

Saddle-shaped zinc porphyrin nanorings are utilized as light-harvesting materials. To achieve high performance, both fast charge transfer and slow charge recombination are required. Fast transfer favors efficient separation of exciton into free carriers, enhancing photocurrent. Slow recombination reduces charge and energy losses. We simulated both processes using time-dependent self-consistent-charge density functional tight binding theory combined ...

Added: November 19, 2025

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Macromolecular porphyrin nanorings are receiving significant attention because of their excellent optoelectronic properties. However, their efficiencies as potential solar materials are significantly affected by nonradiative charge recombination. To understand the recombination mechanism by alternating structural parameters and using tight-binding nonadiabatic molecular dynamics, we demonstrate that charge recombination depends strongly on the mode of the linker ...

Added: November 19, 2025