Kanad Majumder | Searcharxiv

arXiv2026

Persistent singlet electronic character in the multiexcitonic triplet-pair state of strongly coupled pentacene singlet fission dimers

Singlet fission converts an optically excited singlet state into a spin-entangled triplet pair state (TT$_1$)$^1$ that can, in principle, yield two free triplets for photovoltaics and/or a polarized high spin state for quantum technologies. Synthetically tunable templates suggest that the above photophysics is governed by a subtle but poorly understood interplay of molecular motifs, geometry and structural fluctuations. Here, we investigate the (TT$_1$)$^1$ state in a library of conformationally flexible pentacenic dimers, where a (TT$_1$)$^1$-specific near-IR spectral feature is readily available. Using a suite of polarization-controlled impulsive optical spectroscopies, we find that (TT$_1$)$^1$ formation is specific to planar conformations and is accompanied by large nuclear reorganization in the (TT$_1$)$^1$ photoproduct. Introducing polarization anisotropy to track the electronic character of the (TT$_1$)$^1$ species, supported by screened configuration interaction based electronic structure theory, we find that significant singlet-triplet electronic mixing is persistent throughout its evolution. This behavior is universal across diverse bridging motifs and indicates that, once the triplet pair is strongly bound, neither substantial nuclear reorganization nor structural fluctuations on longer timescales are sufficient to suppress persistent singlet-triplet electronic mixing, such that triplet-pair decorrelation is outcompeted by its decay. Our observations establish polarization-selective pump-probe and anisotropy as a direct optical probe of triplet pair decorrelation, complementary to spin-selective measurements at longer timescales.

physics.chem-ph↗

arXiv2023

Heterogeneous Singlet Fission in a Covalently Linked Pentacene Dimer

Molecular dimers are widely utilized as a tool to investigate the structure-property relationships behind the complex photophysical processes of condensed-phase systems, where structural tuning remains a challenge. This approach often implicitly treats the dimers as static, with their relevant state energies and couplings determined by their optimized geometry. Here, we consider the shortcomings of this approach: dimers are more accurately treated as dynamic model systems, with the potential for significant conformational heterogeneity that evolves in time and is intimately connected with interchromophore coupling strengths. We highlight this concept in the singlet fission dynamics of a pentacene dimer that is covalently linked through phenyl-diketopyrrolopyrrole and acetylene bridges. Unrestricted rotations lead to a vast array of rotational conformers in the ground state. Consequently, we find that every step in the cascade of singlet fission processes - triplet-pair formation from S1, triplet-pair recombination, spin evolution within the pair, and free triplet formation - is qualitatively and quantitatively altered by the conformer geometry. At room temperature, we find evidence of dynamic interconversion between conformers on the multiple TT surfaces. Measurements in frozen solution at 150 K emphasize the significance of static disorder. Our data reveals the presence of sub-populations that result in excitation-dependent electron spin polarization. These phenomena demand consideration of multidimensional potential energy surfaces that define multiple sub-ensembles in the excited state, a picture we refer to as heterogeneous singlet fission. More broadly, our results call into question the general static approach to molecular dimer photophysics, that each step in consecutive excited-state relaxation pathways can be delineated with a single, unique rate constant and yield.

physics.chem-ph↗