Unveiling the intersystem crossing dynamics in N-annulated perylene bisimides.

The efficient population of the triplet excited states in heavy metal-free organic chromophores has been one of the long-standing research problems to molecular photochemists. The negligible spin-orbit coupling matrix elements in the purely organic chromophores and the large singlet-triplet energy gap (ΔES-T) pose a hurdle for ultrafast intersystem crossing (ISC). Herein we report the unprecedented population of triplet manifold in a series of nitrogen-annulated perylene bisimide chromophores (NPBI and Br-NPBI). NPBI is found to have a moderate fluorescence quantum yield (Φf = 68 ± 5%), whereas Br-NPBI showcased a low fluorescence quantum yield (Φf = 2.0 ± 0.6%) in toluene. The femtosecond transient absorption measurements of Br-NPBI revealed ultrafast ISC (kISC = 1.97 × 1010 s-1) from the initially populated singlet excited state to the long-lived triplet excited states. The triplet quantum yields (ΦT = 95.2 ± 4.6% for Br-NPBI, ΦT = 18.7 ± 2.3% for NPBI) calculated from nanosecond transient absorption spectroscopy measurements showed the enhancement in triplet population upon bromine substitution. The quantum chemical calculations revealed the explicit role of nitrogen annulation in tuning the excited state energy levels to favor the ISC. The near degeneracy between the singlet and triplet excited states observed in NPBI and Br-NPBI (ΔES-T = -0.01 eV for NPBI, ΔES-T = 0.03 eV for Br-NPBI) facilitates the spin flipping in the molecules. Nitrogen annulation emerges as a design strategy to open up the ISC pathway and the rate of which can be further enhanced by the substitution of a heavier element.

Excimer evolution hampers symmetry-broken charge-separated states.

Achieving long-lived symmetry-broken charge-separated states in chromophoric assemblies is quintessential for enhanced performance of artificial photosynthetic mimics. However, the occurrence of energy trap states hinders exciton and charge transport across photovoltaic devices, diminishing power conversion efficiency. Herein, we demonstrate unprecedented excimer formation in the relaxed excited-state geometry of bichromophoric systems impeding the lifetime of symmetry-broken charge-separated states. Core-annulated perylenediimide dimers (SC-SPDI2 and SC-NPDI2) prefer a near-orthogonal arrangement in the ground state and a π-stacked foldamer structure in the excited state. The prospect of an excimer-like state in the foldameric arrangement of SC-SPDI2 and SC-NPDI2 has been rationalized by fragment-based excited state analysis and temperature-dependent photoluminescence measurements. Effective electronic coupling matrix elements in the Franck-Condon geometry of SC-SPDI2 and SC-NPDI2 facilitate solvation-assisted ultrafast symmetry-breaking charge-separation (SB-CS) in a high dielectric environment, in contrast to unrelaxed excimer formation (Ex*) in a low dielectric environment. Subsequently, the SB-CS state dissociates into an undesired relaxed excimer state (Ex) due to configuration mixing of a Frenkel exciton (FE) and charge-separated state in the foldamer structure, downgrading the efficacy of the charge-separated state. The decay rate constant of the FE to SB-CS (k FE→SB-CS) in polar solvents is 8-17 fold faster than that of direct Ex* formation (k FE→Ex*) in non-polar solvent (k FE→SB-CS≫k FE→Ex*), characterized by femtosecond transient absorption (fsTA) spectroscopy. The present investigation establishes the impact of detrimental excimer formation on the persistence of the SB-CS state in chromophoric dimers and offers the requisite of conformational rigidity as one of the potential design principles for developing advanced molecular photovoltaics.

Exciton interactions in helical crystals of a hydrogen-bonded eumelanin monomer.

Eumelanin, a naturally occurring group of heterogeneous polymers/aggregates providing photoprotection to living organisms, consist of 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA) building blocks. Despite their prevalence in the animal world, the structure and therefore the mechanism behind the photoprotective broadband absorption and non-radiative decay of eumelanin remain largely unknown. As a small step towards solving the incessant mystery, DHI is crystallized in a non-protic solvent environment to obtain DHI crystals having a helical packing motif. The present approach reflects the solitary directional effect of hydrogen bonds between the DHI chromophores for generating the crystalline assembly and filters out any involvement of the surrounding solvent environment. The DHI single crystals having an atypical chiral packing motif (P212121 Sohncke space group) incorporate enantiomeric zig-zag helical stacks arranged in a herringbone fashion with respect to each other. Each of the zig-zag helical stacks originates from a bifurcated hydrogen bonding interaction between the hydroxyl substituents in adjacent DHI chromophores which act as the backbone structure for the helical assembly. Fragment-based excited state analysis performed on the DHI crystalline assembly demonstrates exciton delocalization along the DHI units that connect each enantiomeric helical stack while, within each stack, the excitons remain localized. Fascinatingly, over the time evolution for generation of single-crystals of the DHI-monomer, mesoscopic double-helical crystals are formed, possibly attributed to the presence of covalently connected DHI trimers in chloroform solution. The oligomeric DHI (in line with the chemical disorder model) along with the characteristic crystalline packing observed for DHI provides insights into the broadband absorption feature exhibited by the chromophore.

Access to the triplet excited states of organic chromophores.

Over the last several decades, exploring the pathways to access the triplet excited states of organic chromophores has been a stimulating area of research. Among the numerous photoinduced processes in organic chromophores, analysis of intersystem crossing (ISC) dynamics has received immense attention. The ISC process involves a spin-forbidden horizontal transition from an excited singlet state to a higher vibrational level of the isoenergetic triplet state. Generally, ISC necessitates a strong driving force from efficient spin-orbit coupling (SOC) between the singlet and triplet wavefunctions. The magnitude of SOC can be tuned by the substituent groups (e.g. heavy atoms, carbonyl moieties) or by the out-of-plane vibrational modes in the chromophores. Besides the SOC induced ISC pathway, triplet excited states are also realised in organic chromophores through singlet fission or via charge recombination. Accessing the triplet manifold in π-conjugated systems would also include a possible evolution to more aromatically stable configurations in the excited states, an emerging area that needs attention. In the aforesaid mechanisms, the molecular architecture and/or packing arrangement of the chromophores are vital for the effective population of triplet states. We, herein, present a collection of synthetic, spectroscopic and theoretical investigations that provide insights into the diverse pathways to access triplet excited states in organic chromophores. We believe this tutorial review would prove beneficial for researchers to achieve triplet excited states of organic chromophores for numerous biochemical and optoelectronic applications.