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Ajith Ravi Mallia

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Papers by Ajith Ravi Mallia

Research paper thumbnail of Prolonged Charge Separated States in Twisted Stacks of All-Carbon Donor and Acceptor Chromophores

The Journal of Physical Chemistry Letters, 2016

Twisted donor-on-donor and acceptor-on-acceptor bicontinuous assembly in all-carbon pyren-1-ylace... more Twisted donor-on-donor and acceptor-on-acceptor bicontinuous assembly in all-carbon pyren-1-ylaceanthrylene (PA) dyad extends the survival time of the photoinduced radical ion-pair intermediates. Aceanthrylene, a functional analog of C70, acts as a versatile electron acceptor owing to its high electron affinity and visible light absorption. Antithetical trajectories of the excitons in the nonparallel π-ways led to persistent radical ion-pair intermediates in aggregated (τcr(A) ∼ 1.28 ns) vs monomeric (τcr(M) ≤ 110 fs) PA dyad as observed using femtosecond transient absorption spectroscopy. Marcus theory of charge transfer rates predicts an ambipolar transport characteristic in crystalline PA, thereby endorsing PA as an all-carbon DA hybrid for nonfullerene photovoltaic applications.

Research paper thumbnail of Nonparallel Stacks of Donor and Acceptor Chromophores Evade Geminate Charge Recombination

Journal of the American Chemical Society, 2015

We report a nonparallel stacked arrangement of donor–acceptor (D–A) pairs for prolonging the life... more We report a nonparallel stacked arrangement of donor–acceptor (D–A) pairs for prolonging the lifetime of photoinduced charge-separated states. Hydrogen–hydrogen steric repulsion in naphthalimide-naphthalene (NIN) dyad destabilizes the planar geometry between the constituent units in solution/ground state. Sterically imposed nonplanar geometry of the dyad allows the access of nonparallel arrangement of the donor and acceptor stacks having triclinic space group in the crystalline state. Antiparallel trajectory of excitons in nonparallel D–A stacks can result in lower probability of geminate charge recombination, upon photoexcitation, thereby resulting in a long-lived charge-separated state. Upon photoexcitation of the NIN dyad, electron transfer from naphthalene to the singlet excited state of naphthalimide moiety results in radical ion pair intermediates that survive >10,000-fold longer in the aggregated state (τcra > 1.2 ns) as compared to that of monomeric dyad (τcrm < 110 fs), monitored using femtosecond transient absorption spectroscopy.

Research paper thumbnail of Effect of temperature on symmetry breaking excited state charge separation: restoration of symmetry at elevated temperature

Physical Chemistry Chemical Physics, 2012

Research paper thumbnail of Light harvesting vesicular donor–acceptor scaffold limits the rate of charge recombination in the presence of an electron donor

Energy & Environmental Science, 2014

This work highlights the utility of π–π stacked self-assembly for enhanced survival time of charg... more This work highlights the utility of π–π stacked self-assembly for enhanced survival time of charge transfer intermediates upon photoexcitation of donor–acceptor systems.

Research paper thumbnail of Prolonged Charge Separated States in Twisted Stacks of All-Carbon Donor and Acceptor Chromophores

The Journal of Physical Chemistry Letters, 2016

Twisted donor-on-donor and acceptor-on-acceptor bicontinuous assembly in all-carbon pyren-1-ylace... more Twisted donor-on-donor and acceptor-on-acceptor bicontinuous assembly in all-carbon pyren-1-ylaceanthrylene (PA) dyad extends the survival time of the photoinduced radical ion-pair intermediates. Aceanthrylene, a functional analog of C70, acts as a versatile electron acceptor owing to its high electron affinity and visible light absorption. Antithetical trajectories of the excitons in the nonparallel π-ways led to persistent radical ion-pair intermediates in aggregated (τcr(A) ∼ 1.28 ns) vs monomeric (τcr(M) ≤ 110 fs) PA dyad as observed using femtosecond transient absorption spectroscopy. Marcus theory of charge transfer rates predicts an ambipolar transport characteristic in crystalline PA, thereby endorsing PA as an all-carbon DA hybrid for nonfullerene photovoltaic applications.

Research paper thumbnail of Nonparallel Stacks of Donor and Acceptor Chromophores Evade Geminate Charge Recombination

Journal of the American Chemical Society, 2015

We report a nonparallel stacked arrangement of donor–acceptor (D–A) pairs for prolonging the life... more We report a nonparallel stacked arrangement of donor–acceptor (D–A) pairs for prolonging the lifetime of photoinduced charge-separated states. Hydrogen–hydrogen steric repulsion in naphthalimide-naphthalene (NIN) dyad destabilizes the planar geometry between the constituent units in solution/ground state. Sterically imposed nonplanar geometry of the dyad allows the access of nonparallel arrangement of the donor and acceptor stacks having triclinic space group in the crystalline state. Antiparallel trajectory of excitons in nonparallel D–A stacks can result in lower probability of geminate charge recombination, upon photoexcitation, thereby resulting in a long-lived charge-separated state. Upon photoexcitation of the NIN dyad, electron transfer from naphthalene to the singlet excited state of naphthalimide moiety results in radical ion pair intermediates that survive >10,000-fold longer in the aggregated state (τcra > 1.2 ns) as compared to that of monomeric dyad (τcrm < 110 fs), monitored using femtosecond transient absorption spectroscopy.

Research paper thumbnail of Effect of temperature on symmetry breaking excited state charge separation: restoration of symmetry at elevated temperature

Physical Chemistry Chemical Physics, 2012

Research paper thumbnail of Light harvesting vesicular donor–acceptor scaffold limits the rate of charge recombination in the presence of an electron donor

Energy & Environmental Science, 2014

This work highlights the utility of π–π stacked self-assembly for enhanced survival time of charg... more This work highlights the utility of π–π stacked self-assembly for enhanced survival time of charge transfer intermediates upon photoexcitation of donor–acceptor systems.

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