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Tin halide perovskite (Sn-HPs) photovoltaics could potentially equal or exceed the performance of their more toxic Pb-based analogues if defect state densities, particularly originating from the presence of Sn4+, can be significantly decreased. Numerous additives are incorporated into Sn-HPs to minimize the amount of Sn4+, including SnF2, reducing agents such as hydrazine derivatives, and various antioxidants. Despite the frequent use of additives to reduce Sn4+ content, there is limited understanding of how they function and consequently limited guidance for the development of new additives. Herein, we use cyclic voltammetry to probe the redox behavior of SnI2, SnI4, Sn-HP precursor solutions, and 18 different additives. Through 119Sn NMR measurements we show that hydrochloride containing additives undergo halide exchange with SnI4 to form SnIxCly, which results in decreased Sn4+ concentrations and less p-type character in the Sn-HP films. We find that the most effective additive at lowering the Sn4+ content in FASnI3 is not capable of reducing SnI4 or forming SnIxCly, but rather it acts as a sacrificial and coordinating antioxidant. In general, when selecting additives for Sn-HPs it is important to account for the redox potential, coordination with Sn species, ability to react with oxygen, and the potential for halide exchange. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A ditopic bis(pyrazolyl)methane-based ligand has been prepared. • A μ 4 -oxido-bridged tetranuclear Cu(II) complex has been obtained. • The complex has been characterized by single crystal X-ray diffraction. • The catecholase activity of the complex was investigated. Abstract A new tetranuclear copper(II) complex, {But-C 6 H 2 (O)[CH = N-CH 2 -CH(pz) 2 ] 2 } 2 Cu 4 (μ 4 -O)(OAc) 4 (L 2 Cu 4 (μ 4 -O)(OAc) 4 , pz = pyrazolyl ring) has been prepared from the condensation reaction of 4- tert -butyl-2,6-diformylphenol with two equivalents of bis(pyrazolyl)ethanamine moieties in the presence of two equivalents of copper(II) acetate. The complex has been characterized by X-ray diffraction studies in solid state, as well as by UV–Vis, IR, and ESI spectroscopies. The structure of this inverse coordination complex consists of a central oxygen ion surrounded by four copper(II) cations residing in the corners of a distorted tetrahedron; the remaining coordination sites of the Cu2+ ions are filled by imine donors and acetate counter-ions, leaving the bis(pyrazolyl)methane donor groups uncoordinated to the copper(II) centers. In contrast to the solid-state structure, this compound was found to be dinuclear in solution, LCu 2 (OAc) 2 (OH). The complex catalyzes the oxidation of 3,5-di- tert -butylcatechol (DTBC) and 4- tert -butylcatechol (TBC) to their corresponding quinones. The catalytic mechanism was investigated using DTBC as a substrate, and it was found that the oxidation reaction occurs via two different pathways, one involving molecular oxygen and the other hydrogen peroxide as oxidants. [ABSTRACT FROM AUTHOR]

Unlike single‐component 2D metal halide perovskites (MHPs) exhibiting sharp excitonic photoluminescence (PL), a broadband PL emerges in mixed Pb‐Sn 2D lattices. Two physical models –self‐trapped exciton and defect‐induced Stokes‐shift – are proposed to explain this unconventional phenomenon. However, the explanations provide limited rationalizations without consideration of the formidable compositional space, and thus, the fundamental origin of broadband PL remains elusive. Herein, the high‐throughput automated experimental workflow is established to systematically explore the broadband PL in mixed Pb‐Sn 2D MHPs, employing PEA (Phenethylammonium) as a model cation known to work as a rigid organic spacer. Spectrally, the broadband PL becomes further broadened with rapid PEA2PbI4 phase segregation with increasing Pb concentrations during early‐stage crystallization. Counterintuitively, MHPs with high Pb concentrations exhibit prolonged PL lifetimes. Hyperspectral microscopy identifies substantial PEA2PbI4 phase segregation in those films, hypothesizing that the establishment of charge transfer excitons by the phase segregation upon crystallization at high‐Pb compositions results in distinctive PL properties. These results indicate that two independent mechanisms—defect‐induced Stoke‐shifts and the establishment of charge transfer excitons by phase segregation—coexist which significantly correlates with the Pb:Sn ratio, thereby simultaneously contributing to the broadband PL emission in 2D mixed Pb‐Sn HPs. [ABSTRACT FROM AUTHOR]