Porphyrin-Based Hole-Transporting Materials for Perovskite Solar Cells: Boosting Performance with Smart Synthesis.

Perovskite solar cells (PSCs) are becoming a promising and revolutionary advancement within the photovoltaic field globally. Continuous improvement in efficiency, straightforward processing methods, and use of lightweight and cost-effective materials represent superior features, among other notable aspects. Still, long-term stability and durability are issues to address to facilitate widespread commercial adoption and practical application prospects. Research has focused on overcoming these challenges, and charge transport materials play a critical role in determining charge dynamics, photovoltaic performance, and device stability. Conventional hole-transporting materials (HTMs), spiro-OMeTAD and PTAA, contribute to remarkable power conversion efficiencies owing to high thin-film quality and matched energy alignment. However, they often show a high material cost, low carrier mobility, and poor stability, which greatly limit their practical applications. Now, this review outlines recent advances in synthetic approaches to porphyrin-based HTMs to tune the charge dynamics by optimizing their molecular structures and properties. The main structural features comprise porphyrins of A4-type, trans A2B2-type, and photosynthetic pigment analogues. Strategies include well-established routes to provide the required macrocycles, such as condensation of pyrrole or dipyrromethanes with suitable aldehydes, metalation of the porphyrin inner core, and postfunctionalization of peripheral positions. These functionalizations involve conventional procedures (e.g., halogenation, esterification, transesterification, nucleophilic oxidation, reduction, and nucleophilic substitution) as well as metal-catalyzed ones such as Suzuki-Miyaura, Sonogashira, Buchwald-Hartwig, and Ullmann cross-coupling reactions. As HTMs can also protect the perovskite layer from the external environment, porphyrin structures play a pivotal role in chemical, mechanical, and environmental stability, with their high hydrophobicity ability as the most significant parameter. The impact of porphyrins on the hole hopping of other HTMs while acting as an additive or an interlayer, passivating defects, and improving charge transport is also highlighted to provide real insights into ways to develop efficient and stable porphyrin-based materials for PSCs. This perspective aims to guide the scientific community in the design of new porphyrin molecules to place PSCs as an outperformer in photovoltaic technologies.

C-N linked donor type porphyrin derivatives: unrevealed hole-transporting materials for efficient hybrid perovskite solar cells.

A new series of Zn(II) and Cu(II)-based porphyrin complexes 5a and 5b doubly functionalised with carbazole units were developed to be used as hole-transporting materials (HTMs) in perovskite solar cells (PSCs). These complexes were obtained via a nucleophilic substitution reaction mediated by PhI(OAc)2/NaAuCl4·2H2O, or using C-N transition metal-assisted coupling. The hole extraction capability of 5a and 5b was assessed using cyclic voltammetry; this study confirmed the better alignment of the Zn(II) complex 5a with the perovskite valence band level, compared to the Cu(II) complex 5b. The optimised geometry and molecular orbitals of both complexes also corroborate the higher potential of 5a as a HTM. Photoluminescence characterisation showed that the presence of 5a and 5b as HTMs on the perovskite surface resulted in the quenching of the emission, matching the hole transfer phenomenon. The photovoltaic performance was evaluated and compared with those of reference cells made with the standard HTM spiro-OMeTAD. The optimised 5-based devices showed improvements in all photovoltaic characteristics; their open circuit voltage (Voc) reached close to 1 V and short-circuit current density (Jsc) values were 13.79 and 9.14 mA cm-2 for 5a and 5b, respectively, disclosing the effect of the metallic centre. A maximum power conversion efficiency (PCE) of 10.01% was attained for 5a, which is 65% of the PCE generated by using the spiro-OMeTAD reference. This study demonstrates that C-N linked donor-type porphyrin derivatives are promising novel HTMs for developing efficient and reproducible PSCs.

Bis-thiobarbiturates as Promising Xanthine Oxidase Inhibitors: Synthesis and Biological Evaluation.

Xanthine oxidase (XO) is the enzyme responsible for the conversion of endogenous purines into uric acid. Therefore, this enzyme has been associated with pathological conditions caused by hyperuricemia, such as the disease commonly known as gout. Barbiturates and their congeners thiobarbiturates represent a class of heterocyclic drugs capable of influencing neurotransmission. However, in recent years a very large group of potential pharmaceutical and medicinal applications have been related to their structure. This great diversity of biological activities is directly linked to the enormous opportunities found for chemical change off the back of these findings. With this in mind, sixteen bis-thiobarbiturates were synthesized in moderate to excellent reactional yields, and their antioxidant, anti-proliferative, and XO inhibitory activity were evaluated. In general, all bis-thiobarbiturates present a good antioxidant performance and an excellent ability to inhibit XO at a concentration of 30 µM, eight of them are superior to those observed with the reference drug allopurinol (Allo), nevertheless they were not as effective as febuxostat. The most powerful bis-thiobarbiturate within this set showed in vitro IC50 of 1.79 µM, which was about ten-fold better than Allo inhibition, together with suitable low cytotoxicity. In silico molecular properties such as drug-likeness, pharmacokinetics, and toxicity of this promising barbiturate were also analyzed and herein discussed.