Easy access to strongly fluorescent higher homologues of BODIPY.

We present the easy and high yield synthesis of several group 13 MesDPM compounds (Al-In) with alkyl substituents at the metal atom. All these compounds were fully characterized using techniques including X-ray diffraction analysis and photoluminescence measurements. It shows that for aluminium and gallium pronounced green fluorescence is observed, which is absent for indium. DFT calculations confirm that the first electronic transition corresponds to a ligand-based π-π* transition.

Enhanced Circular Dichroism and Polarized Emission in an Achiral, Low Band Gap Bismuth Iodide Perovskite Derivative.

Lead halide perovskites and related main-group halogenido metalates offer unique semiconductor properties and diverse applications in photovoltaics, solid-state lighting, and photocatalysis. Recent advances in incorporating chiral organic cations have led to the emergence of chiral metal-halide semiconductors with intriguing properties, such as chiroptical activity and chirality-induced spin selectivity, enabling the generation and detection of circularly polarized light and spin-polarized electrons for applications in spintronics and quantum information. However, understanding the structural origin of chiroptical activity remains challenging due to macroscopic factors and experimental limitations. In this work, we present an achiral perovskite derivative [Cu2(pyz)3(MeCN)2][Bi3I11] (CuBiI; pyz = pyrazine; MeCN = acetonitrile), which exhibits remarkable circular dichroism (CD) attributed to the material's noncentrosymmetric nature. CuBiI features a unique structure as a poly-threaded iodido bismuthate, with [Bi3I11]2- chains threaded through a cationic two-dimensional coordination polymer. The material possesses a low, direct optical band gap of 1.70 eV. Notably, single crystals display both linear and circular optical activity with a large anisotropy factor of up to 0.16. Surprisingly, despite the absence of chiral building blocks, CuBiI exhibits a significant degree of circularly polarized photoluminescence, reaching 4.9%. This value is comparable to the results achieved by incorporating chiral organic molecules into perovskites, typically ranging from 3-10% at zero magnetic field. Our findings provide insights into the macroscopic origin of CD and offer design guidelines for the development of materials with high chiroptical activity.

Selective and benign alkylation of sulfido-oxo stannate clusters with propyl, pentyl, or hexyl substituents.

Chalcogenido metalate compounds that are based on tetrahedral clusters have been extensively studied in recent years due to their rich structural chemistry and uncommon chemical and physical properties. Recently it was shown that partial butylation of the inorganic cluster core by ionothermal reactions allowed access to tetrahedral sulfido-oxo stannate clusters with reasonable solubility in conventional solvents at the retainment of their opto-electronic features. We have expanded this mild alkylation approach, and herein report success in receiving the first sulfido-oxo stannate clusters that are selectively propylated, pentylated, and hexylated. This was achieved in a unique way by preparing symmetrically 1,3-substituted imidazolium bromides in preparative scale and using them as both the reaction medium and alkylatoin reagent. We discuss the effect of the organic groups attached to the cluster and present in the counterions of the products on the compounds' structural and opto-electronic properties.

Optical Properties and Metal-Dependent Charge Transfer in Iodido Pentelates.

Lead-free heavy halogenido metalates are currently under intense investigation, as they show similarly promising semiconducting properties as their famous but toxic lead relatives. A major interest in this regard is the understanding and control of optical properties with the goal of designing highly efficient photoconducting materials. Here, we present two isostructural iodido pentelates (Hpyz)3 E2 I9 ⋅ 2H2 O (pyz=pyrazine; E=Sb, Bi). Both compounds are stable up to 100 °C. We observe an inverted order of band gap sizes, 1.91 eV and 1.98 eV for the antimony and bismuth compound, respectively, compared to similar pairs of compounds. We use DFT calculations to confirm that this surprising finding can be traced back to the presence of charge transfer excitations in both compounds.

Establishing Family Relations in Group 15 Halogenido Metalates with the Largest Molecular Antimony Iodide Anion.

Studying structurally related families of compounds is a valuable tool in understanding and predicting material properties and has been extensively used for metal halide perovskites. Due to the variable anion structures in group 15 halogenido metalates, similar family relations are still largely missing. Herein, we present compounds featuring the [Sb2n I6n+4 ]4- family of anions, including the first n=5 member in [Hpyz]4 [Sb10 I34 ] (Hpyz=pyrazinium), which contains the largest halogenido pentelate anion reported to date. The optical properties of compounds featuring n=1-5 anions show a clear trend as well as an outlier, a low band gap of 1.72 eV for [Hpyz]4 [Sb10 I34 ], that can be well understood using quantum chemical investigations. Also using SbI3 and [H2 NMe2 ]3 [SbI6 ], a compound featuring a single octahedral [SbI6 ]3- unit, as limiting cases, we show that structure-property relationships can be established in group 15 halogenido metalates in a similar way as in metal halide perovskites, thus providing a framework for understanding new and known compounds in this emerging class of materials.

Crystalline chalcogenidometalate-based compounds from uncommon reaction media.

Chalcogenides are one of the most versatile inorganic materials families, further subdivided into a large variety of specific groups of compounds, ranging from neat binary or multinary solids and nanoparticles of the same formal compositions, both in crystalline or non-crystalline form, to complicated open-framework structures and cluster compounds, also including organ(ometall)ic derivates of the latter. The large variety regarding both the compositions and the structures is associated with an enormous variety of properties, ranging from simple or high-tech pigments through a multitude of opto-electronic devices and electrolytes to materials for ion separation or high-sophisticated catalysts. Naturally, this also goes hand in hand with a corrosponding breadth of synthesis strategies. Traditionally, chalcogenides have been accessed via high-temperature methods, which continuously have been replaced by lower-temperature approaches for economical and ecological reasons. Moreover, more recent methods also showed that new types of chalcogenide materials can be obtained under such milder conditions that are not accessible via traditional routes. To shed light onto one of the numerous families of chalcogenides, this feature article summarizes current achievements in the generation of multinary chalcogenidometallate-based clusters and networks via non-classical routes, using ionic liquids, surfactants, or hydrazine as reaction media at moderately elevated termperature.

Highly Soluble Supertetrahedra upon Selective Partial Butylation of Chalcogenido Metalate Clusters in Ionic Liquids.

Supertetrahedral clusters have been reported in two generally different types so far: one type possessing an organic ligand shell, no or low charges, and high solubility, while the other cluster type is ligand-free with usually high charges and low or no solubility in common solvents. The latter is a tremendous disadvantage regarding further use of the clusters in solution. However, as organic substituents usually broaden the HOMO-LUMO gaps, which cannot be overcompensated by the (limited) cluster sizes, a full organic shielding comes along with drawbacks regarding opto-electronic properties. We therefore sought to find a way of generating soluble clusters with a minimum number of organic substituents. Here, we present the synthesis and full characterization of two salts of [Sn10 O4 S16 (SBu)4 ]4- that are high soluble in CH2 Cl2 or CH3 CN, which includes first NMR and mass spectra obtained from solutions of such salts with mostly inorganic supertetrahedral clusters. The optical absorption properties of this new class of compounds indicates nearly unaffected band gaps. The synthetic approach and the spectroscopic findings were rationalized and explained by means of high-level quantum chemical studies.