with outstanding optoelectronic properties. [1] In 2009, these materials were introduced in solar cells and have since established a striking increase in performance, reaching over 22% in stateof-the-art devices. [2] Here, the perovskite absorber is sandwiched between two selective charge extraction layers, that transport the charges to the electrodes. [3] Although efficient inorganic hole transporting materials (HTMs) have been reported, [4] the most well-known HTMs are the organic materials 2,2′,7,7′-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9′spirobifluorene (Spiro-OMeTAD) and polytriarylamine (PTAA). Alternatives that compete in performance have been published, [5][6][7] however, just like Spiro-OMeTAD and PTAA, most of these materials are synthesized in multistep synthetic procedures, involving (transition) metal catalyzed cross-coupling reactions, stringent reaction conditions and extensive product purification. This results in a relative high material cost, consequently leading to a significant contribution to the total device cost. [5,8,9] Additionally, the tedious synthesis hampers large State-of-the-art perovskite-based solar cells employ expensive, organic hole transporting materials (HTMs) such as Spiro-OMeTAD that, in turn, limits the commercialization of this promising technology. Herein an HTM (EDOT-Amide-TPA) is reported in which a functional amide-based backbone is introduced, which allows this material to be synthesized in a simple condensation reaction with an estimated cost of <$5 g −1 . When employed in perovskite solar cells, EDOT-Amide-TPA demonstrates stabilized power conversion efficiencies up to 20.0% and reproducibly outperforms Spiro-OMeTAD in direct comparisons. Time resolved microwave conductivity measurements indicate that the observed improvement originates from a faster hole injection rate from the perovskite to EDOT-Amide-TPA. Additionally, the devices exhibit an improved lifetime, which is assigned to the coordination of the amide bond to the Li-additive, offering a novel strategy to hamper the migration of additives. It is shown that, despite the lack of a conjugated backbone, the amide-based HTM can outperform state-of-the-art HTMs at a fraction of the cost, thereby providing a novel set of design strategies to develop new, low-cost HTMs.

A series of azomethine-based HTMs is synthesized using simple condensation chemistry. Their photovoltaic performance and moisture barrier properties are presented.

Organocatalysis is a powerful approach to extend and (enantio‐) selectively modify molecular structures. Adapting this concept to the Early Earth scenario offers a promising solution to explain their evolution into a complex homochiral world. Herein, we present a class of imidazolidine‐4‐thione organocatalysts, easily accessible from simple molecules available on an Early Earth under highly plausible prebiotic reaction conditions. These imidazolidine‐4‐thiones are readily formed from mixtures of aldehydes or ketones in presence of ammonia, cyanides and hydrogen sulfide in high selectivity and distinct preference for individual compounds of the resulting catalyst library. These organocatalysts enable the enantioselective α‐alkylation of aldehydes under prebiotic conditions and show activities that correlate with the selectivity of their formation. Furthermore, the crystallization of single catalysts as conglomerates opens the pathway for symmetry breaking.

The acetate-initiated aliphatic isocyanate trimerization to isocyanurate was investigated by state-of-the-art analytical and computational methods. Although the common cyclotrimerization mechanism assumes the consecutive addition of three equivalents of isocyanate to acetate prior to product formation, we found that the underlying mechanism is more complex. In this work, we demonstrate that the product, in fact, is formed via the connection of two unexpected catalytic cycles, with acetate being only the precatalyst. The initial discovery of a precatalyst activation by quantum chemical computations and the resulting first catalysis cycle were corroborated by mass spectrometric and NMR experiments, thereby additionally revealing a catalyst migration to the second catalytic cycle. These results were further confirmed by computations, completing the full mechanistic understanding of this catalytic system. Identification of a side product with undesired properties for final coating applications allows for process optimization in the chemical industry.