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Materials with chiral electronic structures are of great interest. We report a triazatruxene, TAT, molecular semiconductor with chiral alkyl side chains that crystallises from solution to form chirally-stacked columns with a helical pitch of 6 TATs (2.3 nm). These crystals show strong circularly polarised, CP, green photoluminescence, with dissymmetry of 24%. Electronic structure calculations using the full crystal structure, show that this chiral stacking associates angular momentum to the valence and conduction states and thus gives rise to the observed CP luminescence. Free-standing crystals are not useful for active semiconductor devices, but we have discovered that co-sublimation of TAT as the guest in a structurally mismatched host enables the fabrication of thin films where the chiral crystallization is achieved in-situ by thermally-triggered nano-phase segregation of dopant and host whilst preserving the integrity of the film. This enables fabrication of bright (green) organic light-emitting diodes with unexpectedly high external quantum efficiencies of up to 16% and electroluminescence dissymmetries above 10%. These materials and this process method offer significant application potential in spintronics, optical displays and multidimensional optoelectronics.

Optical control and read-out of the ground state spin structure has been demonstrated for defect states in crystalline semiconductors, including the diamond NV- center, and these are promising systems for quantum technologies. Molecular organic semiconductors offer synthetic control of spin placement, in contrast to current limitations in these crystalline systems. Here we report the discovery of spin-optical addressability in a diradical molecule that comprises two trityl radical groups coupled via a fluorene bridge. We demonstrate the three important properties that enable operation as a spin-photon interface: (i) triplet and singlet spin states show photoluminescence peaked at 640 and 700 nm respectively; this allows easy optical measurement of ground state spin. (ii) the ground state spin exchange is small (~60 {\mu}eV) that allows preparation of ground state spin population. This can be achieved by spin-selective excited state intersystem crossing, and we report up to 8% microwave-driven contrast in photoluminescence. (iii) both singlet and triplet manifolds have near-unity photoluminescence quantum yield, which is in contrast to the near-zero quantum yields in prior reports of molecular diradicals. Our results establish these tuneable open-shell organic molecules as a platform to engineer tailor-made spin-optical interfaces.

The family of hybrid organic-inorganic lead-halide perovskites are the subject of intense interest for optoelectronic applications, from light-emitting diodes to photovoltaics to X-ray detectors. Due to the inert nature of most organic molecules, the inorganic sublattice generally dominates the electronic structure and therefore optoelectronic properties of perovskites. Here, we use optically and electronically active carbazole-based Cz-Ci molecules, where Ci indicates an alkylammonium chain and i indicates the number of CH2 units in the chain, varying from 3-5, as cations in the 2D perovskite structure. By investigating the photophysics and charge transport characteristics of (Cz-Ci)2PbI4, we demonstrate a tunable electronic coupling between the inorganic lead-halide and organic layers. The strongest interlayer electronic coupling was found for (Cz-C3)2PbI4, where photothermal deflection spectroscopy results remarkably demonstrate an organic-inorganic charge transfer state. Ultrafast transient absorption spectroscopy measurements demonstrate ultrafast hole transfer from the photoexcited lead-halide layer to the Cz-Ci molecules, the efficiency of which increases by varying the chain length from i=5 to i=3. The charge transfer results in long-lived carriers (10-100 ns) and quenched emission, in stark contrast with the fast (sub-ns) and efficient radiative decay of bound excitons in the more conventional 2D perovskite (PEA)2PbI4, in which phenylethylammonium (PEA) acts as an inert spacer. Electrical charge transport measurements further support enhanced interlayer coupling, showing increased out-of-plane carrier mobility from i=5 to i=3. This study paves the way for the rational design of 2D perovskites with combined inorganic-organic electronic proper-ties through the wide range of functionalities available in the world of organics., Comment: 16 main text pages + 20 supplemental text pages, 5 main text figures + 19 supplemental figures

Amongst the derivatives of 4-biphenylcarboxylic acid and amino acid esters, the crystal structure of 4-biphenylcarboxy-(L)-phenylalaninate is unusual owing to its monoclinic symmetry within a pseudo-orthorhombic lattice. The distortion is described by disparate rotational property around the chiral centers ($\varphi_{\mathrm{chiral}}$ $\simeq$ -129 degrees and 58 degrees) of the two molecules in the asymmetric unit. Each of these molecules comprise of planar biphenyl moieties ($\varphi_{\mathrm{biphenyl}}$ = 0 degrees). Using temperature dependent single crystal X-ray diffraction experiments we show that the compound undergoes a phase transition below $T$ $\sim$ 124 K that is characterized by a commensurate modulation wave vector, $\mathbf{q}$ = $\delta(101)$, $\delta$ = $\frac{1}{2}$. The (3+1) dimensional modulated structure at $T$ = 100 K suggests that the phase transition drives the biphenyl moieties towards non coplanar conformations with significant variation of internal torsion ($\varphi^{\mathrm{max}}_{\mathrm{biphenyl}}$ $\leq$ $20$ degrees). These intramolecular rotations lead to dimerization of the molecular stacks that are described predominantly by intermolecular tilts and small variations in intermolecular distances. Atypical of modulated structures and superstructures of biphenyl and other polyphenyls, the rotations of individual molecules are asymmetric ($\Delta$$\varphi_{\mathrm{biphenyl}}$ $\approx$ 5 degrees) while $\varphi_{\mathrm{biphenyl}}$ of one independent molecule is two to four times larger than the other. Crystal-chemical analysis and phase relations in superspace suggest multiple competing factors involving intramolecular steric factors, intermolecular H--C${\cdot}{\cdot}{\cdot}$C--H contacts and weak C--H${\cdot}{\cdot}{\cdot}$O hydrogen bonds that govern the distinctively unequal torsional property of the molecules.