Carbene‐metal‐amides (CMAs) are a promising family of donor–bridge–acceptor molecular charge‐transfer (CT) emitters for organic light‐emitting diodes. A universal approach is demonstrated to tune the energy of their CT emission. A blueshift of up to 210 meV is achievable in solid state via dilution in a polar host matrix. The origin of this shift has two components: constraint of thermally‐activated triplet diffusion, and electrostatic interactions between guest and polar host. This allows the emission of mid‐green CMA archetypes to be tuned to sky blue without chemical modifications. Monte‐Carlo simulations based on a Marcus‐type transfer integral successfully reproduce the concentration‐ and temperature‐dependent triplet diffusion process, revealing a substantial shift in the ensemble density of states in polar hosts. In gold‐bridged CMAs, this shift does not lead to a significant change in luminescence lifetime, thermal activation energy, reorganization energy, or intersystem crossing rate. These discoveries offer new insight into coupling between the singlet and triplet manifolds in CMA materials, revealing a dominant interaction between states of CT character. The same approach is employed using materials which have been chemically modified to alter the energy of their CT state directly, shifting the emission of sky‐blue chromophores into the practical blue range.

The nature of carbene-metal-amide (CMA) photoluminescence in the solid state is explored through spectroscopic and quantum-chemical investigations on a representative Au-centred molecule. The crystalline phase offers well-defined coplanar geometries-enabling the link between molecular conformations and photophysical properties to be unravelled. We show that a combination of restricted torsional distortion and molecular electronic polarisation blueshift the charge-transfer emission by around 400 meV in the crystalline versus the amorphous phase, through energetically raising the less-dipolar S 1 state relative to S 0 . This blueshift brings the lowest charge-transfer states very close to the localised carbazole triplet state, whose structured emission is observable at low temperature in the polycrystalline phase. Moreover, we discover that the rate of intersystem crossing and emission kinetics are unaffected by the extent of torsional distortion. We conclude that more coplanar triplet equilibrium conformations control the photophysics of CMAs.

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Abstract-One challenge in studying nanodielectric composites is to produce reliable, reproducible samples. A common strategy to suppress aggregation and make the particles more compatible with the polymer matrix is to modify the nanoparticle surface chemistry but, often, evaluation of the effectiveness of the chosen surface functionalization process can prove difficult. In this paper the emphasis is on feasible ways to monitor the production of silane coupled nanosilica low density polyethylene (LDPE) composites, using Fourier transform infrared spectroscopy (FTIR) and thermal gravimetric analysis (TGA). The AC-breakdown properties of the resulting composites is studied and the field dependency of the DCconductivity is measured and also calculated using a space charge limited conduction (SCLC) model together with densities of states obtained from ab initio calculations. For composites containing 13 wt% of nanosilica, breakdown strengths some 18 % higher than that of the unfilled LDPE were obtained. However, the results are not stable over time. This appears to be related to how extensively the composite is dried at elevated temperatures under vacuum.

Combined molecular dynamics (MD) and quantum mechanics (QM) simulation procedures have gained popularity in modeling the spectral properties of functional organic molecules. However, the potential energy surfaces used to propagate long-time scale dynamics in these simulations are typically described using general, transferable force fields designed for organic molecules in their electronic ground states. These force fields do not typically include spectroscopic data in their training, and importantly, there is no general protocol for including changes in geometry or intermolecular interactions with the environment that may occur upon electronic excitation. In this work, we show that parameters tailored for thermally activated delayed fluorescence (TADF) emitters used in organic light-emitting diodes (OLEDs), in both their ground and electronically excited states, can be readily derived from a small number of QM calculations using the QUBEKit (QUantum mechanical BEspoke toolKit) software and improve the overall accuracy of these simulations.