RESUMEN
The functional properties of organic semiconductors are defined by the interplay between optically bright and dark states. Organic devices require rapid conversion between these bright and dark manifolds for maximum efficiency, and one way to achieve this is through multiexciton generation (S1â1TT). The dark state 1TT is typically generated from bright S1 after optical excitation; however, the mechanistic details are hotly debated. Here we report a 1TT generation pathway in which it can be coherently photoexcited, without any involvement of bright S1. Using <10-fs transient absorption spectroscopy and pumping sub-resonantly, 1TT is directly generated from the ground state. Applying this method to a range of pentacene dimers and thin films of various aggregation types, we determine the critical material properties that enable this forbidden pathway. Through a strikingly simple technique, this result opens the door for new mechanistic insights into 1TT and other dark states in organic materials.
RESUMEN
Covalent dimers, particularly pentacenes, are the dominant platform for developing a mechanistic understanding of intramolecular singlet fission (iSF). Numerous studies have demonstrated that a photoexcited singlet state in these structures can rapidly and efficiently undergo exciton multiplication to form a correlated pair of triplets within a single molecule, with potential applications from photovoltaics to quantum information science. One of the most significant barriers limiting such dimers is the fast recombination of the triplet pair, which prevents spatial separation and the formation of long-lived triplet states. There is an ever-growing need to develop general synthetic strategies to control the evolution of triplets following iSF and enhance their lifetime. Here, we rationally tune the dihedral angle and interchromophore separation between pairs of pentacenes in a systematic series of bridging units to facilitate triplet separation. Through a combination of transient optical and spin-resonance techniques, we demonstrate that torsion within the linker provides a simple synthetic handle to tune the fine balance between through-bond and through-space interchromophore couplings that steer iSF. We show that the full iSF pathway from femtosecond to microsecond timescales is tuned through the static coupling set by molecular design and structural fluctuations that can be biased through steric control. Our approach highlights a straightforward design principle to generate paramagnetic spin pair states with higher yields.
RESUMEN
Harvesting long-lived free triplets in high yields by utilizing organic singlet fission materials can be the cornerstone for increasing photovoltaic efficiencies potentially. However, except for polyacenes, which are the most studied systems in the singlet fission field, spin-entangled correlated triplet pairs and free triplets born through singlet fission are relatively poorly characterized. By utilizing transient absorption and photoluminescence spectroscopy in supramolecular aggregate thin films consisting of Hamilton-receptor-substituted diketopyrrolopyrrole derivatives, we show that photoexcitation gives rise to the formation of spin-0 correlated triplet pair 1(TT) from the lower Frenkel exciton state. The existence of 1(TT) is proved through faint Herzberg-Teller emission that is enabled by vibronic coupling and correlated with an artifact-free triplet-state photoinduced absorption in the near-infrared. Surprisingly, transient electron paramagnetic resonance reveals that long-lived triplets are produced through classical intersystem crossing instead of 1(TT) dissociation, with the two pathways in competition. Moreover, comparison of the triplet-formation dynamics in J-like and H-like thin films with the same energetics reveals that spin-orbit coupling mediated intersystem crossing persists in both. However, 1(TT) only forms in the J-like film, pinpointing the huge impact of intermolecular coupling geometry on singlet fission dynamics.
RESUMEN
Diketopyrrolopyrrole (DPP)-based molecular semiconductors exhibit intriguing optical and charge transport properties. Herein, we rationally design a series of electronically identical but structurally distinct Hamilton receptor (HR)-based supramolecular assembly of DPP. The HR endows supramolecular assemblies via hydrogen bonding with enhanced structural ordering and excitonic couplings. The mechanism of supramolecular self-assembly was probed by diffusion ordered spectroscopy (DOSY) nuclear magnetic resonance (NMR) and solid-state IR spectroscopy studies. We investigated the morphology of self-assembly, photophysical and electrochemical properties and compared them with the identical DPP molecular structures without HRs. The microstructure of self-assembly was probed with atomic force microscopy in thin films. Subsequently, the influence of solid-state packing was studied by single-crystal X-ray diffraction. The single-crystal structure of HR-TDPP-C20 reveals slipped stack arrangements between the two neighboring chromophores with π-π stacking distance and slip angle of 3.55 Å and 35.4°, respectively. Notably, the slight torsional angle of 1° between thiophene and lactam rings and small π-π stacking distance suggest a significant intermolecular coupling between thiophene (D) and lactam (A) rings. This intramolecular coupling between two π-π chromophore stacks manifests in their optical properties. In this manuscript, we report rational design and synthesis of supramolecular self-assembly of DPP with a collection of compelling structural and optical properties.