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Control over the stereochemistry of metal–organic cages can give rise to useful functions that are entwined with chirality, such as stereoselective guest binding and chiroptical applications. Here, we report a chiral CuI12L4pseudo-octahedral cage that self-assembled from condensation of triaminotriptycene, aminoquinaldine, and diformylpyridine subcomponents around CuItemplates. The corners of this cage consist of six head-to-tail dicopper(I) helicates whose helical chirality can be controlled by the addition of enantiopure 1,1′-bi-2-naphthol (BINOL) during the assembly process. Chiroptical and nuclear magnetic resonance (NMR) studies elucidated the process and mechanism of stereochemical information transfer from BINOL to the cage during the assembly process. Initially formed CuI(BINOL)2thus underwent stereoselective ligand exchange during the formation of the chiral helicate corners of the cage, which determined the overall cage stereochemistry. The resulting dicopper(I) helicate corners of the cage were also shown to generate circularly polarized luminescence.

Herein, we report on the charge dynamics of photovoltaic devices based on two novel small-molecule nonfullerene acceptors featuring a central ketone unit. Using ultrafast near-infrared spectroscopy with optical and photocurrent detection methods, we identify one of the key loss channels in the devices as geminate recombination (GR) of interfacial charge transfer states (CTSs). We find that the magnitude of GR is highly sensitive to the choice of solvent and annealing conditions. Interestingly, regardless of these processing conditions, the same lifetime for GR (∼130 ps) is obtained by both detection methods upon decomposing the complex broadband transient optical spectra, suggesting this time scale is inherent and independent of morphology. These observations suggest that the CTSs in the studied material blends are mostly strongly bound, and that charge generation from these states is highly inefficient. We further rationalize our results by considering the impact of the processing on the morphology of the mixed donor and acceptor domains and discuss the potential consequences of the early charge dynamics on the performance of emerging nonfullerene photovoltaic devices. Our results demonstrate that careful choice of processing conditions enables enhanced exciton harvesting and suppression of GR by more than 3 orders of magnitude.

We report smart color-sensing devices of two-dimensional lead halide perovskites that exhibit a graded band gap across the film. We observe that the device short-circuit photocurrent is strongly dependent on excitation wavelength λ, and this arises through photoabsorption at different depths in the sample due to the graded bandgaps present. This λ signature in the response of the device is observed in case of steady-state excitation when incident from the high bandgap side of the film, where a complete reversal in the polarity of the photocurrent Iph(t) is obtained as the excitation wavelength is spanned across the visible spectrum. The transient photocurrent reveals λ-specific response arrived from a combination of positive and negative Iph(t) components. The uniqueness of Iph(t) as a function of incident λ can be utilized to examine spectral purity without dispersive optical elements. An equivalent circuit model description provides a possible glimpse into the physical sources involved in contributing to these features.

We demonstrate a facile route to obtain high and broad-band circular polarization of electroluminescence in single-layer polymer OLEDs. As a light-emitting material we use a donor–acceptor polyfluorene with enantiomerically pure chiral side-chains. We show that upon thermal annealing the polymer self-assembles into a multidomain cholesteric film. By varying the thickness of the polymer emitting layer, we achieve high levels of circular polarization of electroluminescence (up to 40% excess of right-handed polarization), which are the highest reported for polymer OLEDs not using chiral dopants or alignment layers. Mueller matrix ellipsometry shows strong optical anisotropies in the film, indicating that the circular polarization of luminescence arises mainly after the photon has been generated, through selective scattering and birefringence correlated in the direction of the initial linear polarization of the photon. Our work demonstrates that chirally substituted conjugated polymers can combine photonic and semiconducting properties in advanced optoelectronic devices.

We investigate the properties of long-lived species in F8BT films through time-resolved photoluminescence (PL) measurements at room temperature and 10 K. The kinetics consist of an initial exponential decay (τ = 2.26 ns) followed by a weak power-law decay (I(t) ∝ t–1) up to at least 1 ms, both of which depend weakly on temperature. From fluence-dependent PL and ultrafast transient absorption (TA) measurements, we confirm that this emission arises from the recombination of geminate charge-pairs generated through singlet–singlet annihilation. This behavior is a consequence of the donor–acceptor nature of this polymer, which enhances singlet–singlet annihilation and facilitates the formation of long-lived geminate-pairs from energetic singlet states.

Rapid, long-range charge separation in polymer-fullerene organic solar cells (OSCs) enables electrons and holes to move beyond their Coulomb capture radius and overcome geminate recombination. Understanding the nature of charge generation and recombination mechanisms in efficient, nonfullerene-acceptor-based OSCs are critical to further improve device performance. Here we report charge dynamics in an OSC using a perylene diimide (PDI) dimer acceptor. We use transient absorption spectroscopy to track the time evolution of electroabsorption caused by the dipolar electric field generated between electron–hole pairs as they separate after ionization at the donor–acceptor interface. We show that charges separate rapidly (<1 ps) and that free charge carriers are generated very efficiently (∼90% quantum yield). However, in the PDI-based OSC, external charge extraction is impaired by faster nongeminate decay to the ground state and to lower-lying triplet states.

The presence of energetically low-lying triplet states is a hallmark of organic semiconductors. Even though they present a wealth of interesting photophysical properties, these optically dark states significantly limit optoelectronic device performance. Recent advances in emissive charge-transfer molecules have pioneered routes to reduce the energy gap between triplets and “bright” singlets, allowing thermal population exchange between them and eliminating a significant loss channel in devices. In conjugated polymers, this gap has proved resistant to modification. Here, we introduce a general approach to reduce the singlet–triplet energy gap in fully conjugated polymers, using a donor–orthogonal acceptor motif to spatially separate electron and hole wave functions. This new generation of conjugated polymers allows for a greatly reduced exchange energy, enhancing triplet formation and enabling thermally activated delayed fluorescence. We find that the mechanisms of both processes are driven by excited-state mixing between π–π*and charge-transfer states, affording new insight into reverse intersystem crossing.