The electronic properties of MAGeI₃are comparable to MAPbI₃, and it can act as a new lead-free perovskite candidate.

Aggregation‐induced emission (AIE) is a phenomenon where non‐luminescent compounds in solution become strongly luminescent in aggregate and solid phase. It provides a fertile ground for luminescent applications that has rapidly developed in the last 15 years. In this review, we focus on the contributions of theory and computations to understanding the molecular mechanism behind it. Starting from initial models, such as restriction of intramolecular rotations (RIR), and the calculation of non‐radiative rates with Fermi's golden rule (FGR), we center on studies of the global excited‐state potential energy surfaces that have provided the basis for the restricted access to a conical intersection (RACI) model. In this model, which has been shown to apply for a diverse group of AIEgens, the lack of fluorescence in solution comes from radiationless decay at a CI in solution that is hindered in the aggregate state. We also highlight how intermolecular interactions modulate the photophysics in the aggregate phase, in terms of fluorescence quantum yield and emission color.

The mechanism behind aggregation induced emission (AIE) in the prototypical dimethyl tetraphenylsilole (DMTPS) molecule is investigated with ab initio calculations combining the CASSCF and CASPT2 methods with time-dependent DFT. DMTPS is AIE-active because it is strongly fluorescent in the aggregate phase but only weakly in solution. Based on the results, we introduce a restricted access to a conical intersection (RACI) model to explain AIE in DMTPS. According to the RACI model, excited DMTPS in solution can decay to the ground state because there is an energetically available conical intersection, and this explains the weak fluorescence observed experimentally. The reaction coordinate to the intersection involves mainly a twist of the silole ring and a flapping motion of the phenyl substituents. The behaviour in the aggregate phase is simulated by carrying out calculations of one excited DMTPS molecule embedded in a crystal. Because of steric effects, the conical intersection in the crystal is not accessible energetically, and the molecule fluoresces. Thus, the different energy required to access the conical intersection with the ground state in solution and in the crystal explains the AIE phenomenon. Our results are in good agreement with the experimental photophysical properties (absorption and emission wavelength) of DMTPS. They are also in line with recent experimental results for a phosphole analogue of DMTPS showing that fusion of a benzene ring to the phosphole ring increases the lifetime of the excited state in solution (F. Bu, E. Wang, Q. Peng, R. Hu, A. Qin, Z. Zhao and B. Z. Tang, Chem. – Eur. J., 2015, 21, 4440). The present work, together with our previous study on diphenyl dibenzofulvene (Q. Li and L. Blancafort, Chem. Commun., 2013, 49, 5966), suggests that RACI must be quite a general model to explain AIE in medium sized molecules. It is also consistent with the restriction of intramolecular motion (RIM) mechanism introduced recently to explain AIE, since the intramolecular motions responsible for AIE are those leading to the intersection. Knowledge of the reaction coordinate to access the intersection provides useful guidelines for the design of more efficient luminescent compounds.

Perovskite solar cells (PSCs) with organic small molecules as hole transport materials (HTMs) have attracted considerable attention due to their power conversion efficiencies as high as 20%. In the present work, three new spiro-type hole transport materials with spiro-cores, i.e. Spiro-F1, Spiro-F2 and Spiro-F3, are investigated by using density functional theory combined with the Marcus theory and Einstein relation. Based on the calculated and experimental highest occupied molecular orbital (HOMO) levels of 30 reference molecules, an empirical equation, which can predict the HOMO levels of hole transport materials accurately, is proposed. Moreover, a simplified method, in which the hole transport pathways are simplified to be one-dimensional, is presented and adopted to qualitatively compare the molecular hole mobilities. The calculated results show that the perovskite solar cells with the new hole transport materials can have higher open-circuit voltages due to the lower HOMO levels of Spiro-F1 (−5.31 eV), Spiro-F2 (−5.42 eV) and Spiro-F3 (−5.10 eV) compared with that of Spiro-OMeTAD (−5.09 eV). Furthermore, the hole mobilities of Spiro-F1 (1.75 × 10⁻² cm² V⁻¹ s⁻¹) and Spiro-F3 (7.59 × 10⁻³ cm² V⁻¹ s⁻¹) are 3.1 and 1.4 times that of Spiro-OMeTAD (5.65 × 10⁻³ cm² V⁻¹ s⁻¹) respectively, due to small reorganization energies and large transfer integrals. Interestingly, the stability properties of Spiro-F1 and Spiro-F2 are shown to be comparable to that of Spiro-OMeTAD, and the dimers of Spiro-F2 and Spiro-F3 possess better stability than that of Spiro-OMeTAD. Taking into consideration the appropriate HOMO level, improved hole mobility and enhanced stability, Spiro-F1 and Spiro-F3 may become the most promising alternatives to Spiro-OMeTAD. The present work offers a new design strategy and reliable calculation methods towards the development of excellent organic small molecules as HTMs for highly efficient and stable PSCs.

MAGe _0.75 Pb _0.25 I ₃ with the highest theoretical efficiency of 24.24% is superior to MAPbI ₃ , which can become the best candidate.