Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer.

Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

Entangled spin-polarized excitons from singlet fission in a rigid dimer.

Singlet fission, a process that splits a singlet exciton into a biexciton, has promise in quantum information. We report time-resolved electron paramagnetic resonance measurements on a conformationally well-defined acene dimer molecule, TIPS-BP1', designed to exhibit strongly state-selective relaxation to specific magnetic spin sublevels. The resulting optically pumped spin polarization is a nearly pure initial state from the ensemble. The long-lived spin coherences modulate the signal intrinsically, allowing a measurement scheme that substantially removes noise and uncertainty in the magnetic resonance spectra. A nonadiabatic transition theory with a minimal number of spectroscopic parameters allows the quantitative assignment and interpretation of the spectra. In this work, we show that the rigid dimer TIPS-BP1' supports persistent spin coherences at temperatures far higher than those used in conventional superconducting quantum hardware.

Near-Infrared Absorption Features of Triplet-Pair States Assigned by Photoinduced-Absorption-Detected Magnetic Resonance.

Singlet fission proceeds through a manifold of triplet-pair states that are exceedingly difficult to distinguish spectroscopically. Here, we introduce a new implementation of photoinduced-absorption-detected magnetic resonance (PADMR) and use it to understand the excited-state absorption spectrum of a tri-2-pentylsilylethynyl pentadithiophene (TSPS-PDT) film. These experiments allow us to directly correlate magnetic transitions driven by RF with electronic transitions in the visible and near-infrared spectrum with high sensitivity. We find that the new near-infrared excited-state transitions that arise in thin films of TSPS-PDT are correlated with the magnetic transitions of T1, not 5TT. Thus, we assign these features to the excited-state absorption of 1TT, which is depleted when T1 states are driven to a spin configuration that forbids subsequent fusion. These results clarify the disputed origin of triplet-associated near-infrared absorption features in singlet-fission materials and demonstrate an incisive general purpose tool for studying the evolution of high-spin excited states.

Optical readout of singlet fission biexcitons in a heteroacene with photoluminescence detected magnetic resonance.

Molecular spin systems based on photoexcited triplet pairs formed via singlet fission (SF) are attractive as carriers of quantum information because of their potentially pure and controllable spin polarization, but developing systems that offer optical routes to readout as well as initialization is challenging. Herein, we characterize the electron spin magnetic resonance change in the photoluminescence intensity for a tailored organic molecular crystal while sweeping a microwave drive up to 10 GHz in a broadband loop structure. We observe resonant transitions for both triplet and quintet spin sublevel populations showing their optical sensitivity and revealing the zero-field parameters for each. We map the evolution of these spectra in both microwave frequency and magnetic field, producing a pattern of optically detected magnetic resonance (ODMR) peaks. Fits to these data using a suitable model suggest significant spin polarization in this system with orientation selectivity. Unusual excitation intensity dependence is also observed, which inverts the sign of the ODMR signal for the triplet features, but not for the quintet. These observations demonstrate optical detection of the spin sublevel population dictated by SF and intermolecular geometry, and highlight anisotropic and multi-scale dynamics of triplet pairs.

Long-Lived Mixed 2MLCT/MC States in Antiferromagnetically Coupled d3 Vanadium(II) Bipyridine and Phenanthroline Complexes.

Exploration of [V(bpy)3]2+ and [V(phen)3]2+ (bpy = 2,2'-bipyridine; phen = 1,10-phenanthroline) using electronic spectroscopy reveals an ultrafast excited-state decay process and implicates a pair of low-lying doublets with mixed metal-to-ligand charge-transfer (MLCT) and metal-centered (MC) character. Transient absorption (TA) studies of the vanadium(II) species probing in the visible and near-IR, in combination with spectroelectrochemical techniques and computational chemistry, lead to the conclusion that after excitation into the intense and broad visible 4MLCT ← 4GS (ground-state) absorption band (ε400-700 nm = 900-8000 M-1 cm-1), the 4MLCT state rapidly (τisc < 200 fs) relaxes to the upper of two doublet states with mixed MLCT/MC character. Electronic interconversion (τ ∼ 2.5-3 ps) to the long-lived excited state follows, which we attribute to formation of the lower mixed state. Following these initial dynamics, GS recovery ensues with τ = 430 ps and 1.6 ns for [V(bpy)3]2+ and [V(phen)3]2+, respectively. This stands in stark contrast with isoelectronic [Cr(bpy)3]3+, which rapidly forms a long-lived doublet metal-centered (2MC) state following photoexcitation and lacks strong visible GS absorption character. 2MLCT character in the long-lived states of the vanadium(II) species produces geometric distortion and energetic stabilization, both of which accelerate nonradiative decay to the GS compared to [Cr(bpy)3]3+, where the GS and 2MC are well nested. These conclusions are significant because (i) long-lived states with MLCT character are rare in first-row transition-metal complexes and (ii) the presence of a 2MLCT state at lower energy than the 4MLCT state has not been previously considered. The spin assignment of charge-transfer states in open-shell transition-metal complexes is not trivial; when metal-ligand interaction is strong, low-spin states must be carefully considered when assessing reactivity and decay from electronic excited states.