Compact Layers of Hybrid Halide Perovskites Fabricated via the Aerosol Deposition Process : Uncoupling Material Synthesis and Layer Formation

We present the successful fabrication of CH3NH3PbI3 perovskite layers by the aerosol deposition method (ADM). The layers show high structural purity and compactness, thus making them suitable for application in perovskite-based optoelectronic devices. By using the aerosol deposition method we are able to decouple material synthesis from layer processing. Our results therefore allow for enhanced and easy control over the fabrication of perovskite-based devices, further paving the way for their commercialization

Das Dimethylbismut-Kation: Zugang zu dativen Bi-Bi-Bindungen und unkonventionellem Methylaustausch

Die Isolierung einfacher, hochreaktiver metallorganischer Verbindungen von grundlegendem Interesse gehört nach wie vor zu den schwierigsten Aufgaben in der Synthesechemie. Die detaillierte Charakterisierung solcher Verbindungen ist der Schlüssel zum Verständnis neuer Bindungsszenarien und Reaktivitäten. Das Dimethylbismut-Kation, [BiMe2(SbF6)] (1), wurde isoliert und charakterisiert. Seine Reaktion mit BiMe3 ermöglicht den Zugang zu einer bislang unbekannten dativen Bindung, der Bi→Bi-Donor/Akzeptor-Wechselwirkung. Der Austausch von Methylgruppen (der wohl einfachsten Kohlenwasserstoffeinheit) zwischen verschiedenen Metallatomen gehört zu den wichtigsten Reaktionstypen in der metallorganischen Chemie. Die Reaktion von 1 mit BiMe3 ermöglicht einen Methylaustausch über eine Rückseiten-SE2-Reaktion, welche zum ersten Mal im Detail für isolierbare, (pseudo-)homoleptische Hauptgruppenverbindungen untersucht wird

Aminotroponiminates: Coordination Chemistry, Reactivity and Redox Behaviour of Alkali Metal, Silver and Bismut Complexes

Die Koordinationschemie, die Reaktivität und das Redoxverhalten von Alkalimetall-, Silber- und Bismut-Aminotroponiminat(ATI)-Komplexen wurde untersuchtThe coordination chemistry, the reactivity and the redox behaviour of alkali metal, silver and bismut aminotroponiminate (ATI) complexes has been investigate

Dimerization of 2-[(2-((2-aminophenyl)thio)phenyl)amino]-cyclohepta-2,4,6-trien-1-one through hydrogen bonding, C19_{19}H16_{16}N2_2OS

C$_{19}$H$_{16}$N$_2$OS, triclinic, P (1) over bar (no. 2), a= 8.1510(3) angstrom, b = 8.8021(3) angstrom, c =11.3953(5) angstrom, alpha =72.546(2)degrees, beta=84.568(2)degrees, gamma =80.760(2)degrees, V =768.86(5) angstrom(3), Z =2, R$_{gt}$(F) = 0.0491, WR$_{ref}$(F-2) = 0.1494, T =100 K

Cationic Bismuth Aminotroponiminates: Charge Controls Redox Properties

The behavior of the redox‐active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)$_{3}$] and [Bi(ATI)$_{2}$L$_{n}$][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable‐temperature) NMR spectroscopy, line‐shape analysis, and single‐crystal X‐ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann–Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand‐ and metal‐centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored

Cationic Bismuth Aminotroponiminates: Charge Controls Redox Properties

The behavior of the redox‐active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)$_{3}$] and [Bi(ATI)$_{2}$L$_{n}$][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable‐temperature) NMR spectroscopy, line‐shape analysis, and single‐crystal X‐ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann–Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand‐ and metal‐centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored

Rationalizing the Effect of Ligand Substitution Patterns on Coordination and Reactivity of Alkali Metal Aminotroponiminates

A small series of alkali metal aminotroponiminates (ATIs), [M­(ATI^Ph/Ph)­(thf)_<i>n</i>], have been synthesized and fully characterized (M = Li, Na, K). All of these compounds adopt coordination modes that differ from those reported for derivatives with a slightly varied substitution pattern at the ATI ligand (one or two of the N-bound Ph groups substituted by <i>i</i>Pr groups). This leads to an unprecedented ATI coordination mode for the potassium compound [K­(ATI^Ph/​Ph)] and an unusual Li···Ph interaction for the lithium compound [Li­(ATI^Ph/​Ph)]. The influence of the substitution pattern at the ATI ligand on the shape and energy of the frontier orbitals of its sodium complexes has been rationalized by theoretical methods and correlated with experimental results. Analytical techniques applied in this work include NMR spectroscopy, single crystal X-ray diffraction, and DFT calculations

Rationalizing the Effect of Ligand Substitution Patterns on Coordination and Reactivity of Alkali Metal Aminotroponiminates

A small series of alkali metal aminotroponiminates (ATIs), [M­(ATI^Ph/Ph)­(thf)_<i>n</i>], have been synthesized and fully characterized (M = Li, Na, K). All of these compounds adopt coordination modes that differ from those reported for derivatives with a slightly varied substitution pattern at the ATI ligand (one or two of the N-bound Ph groups substituted by <i>i</i>Pr groups). This leads to an unprecedented ATI coordination mode for the potassium compound [K­(ATI^Ph/​Ph)] and an unusual Li···Ph interaction for the lithium compound [Li­(ATI^Ph/​Ph)]. The influence of the substitution pattern at the ATI ligand on the shape and energy of the frontier orbitals of its sodium complexes has been rationalized by theoretical methods and correlated with experimental results. Analytical techniques applied in this work include NMR spectroscopy, single crystal X-ray diffraction, and DFT calculations

Aminotroponiminates: Impact of the NO2_{2} Functional Group on Coordination, Isomerisation, and Backbone Substitution

Aminotroponiminate (ATI) ligands are a versatile class of redox-active and potentially cooperative ligands with a rich coordination chemistry that have consequently found a wide range of applications in synthesis and catalysis. While backbone substitution of these ligands has been investigated in some detail, the impact of electron-withdrawing groups on the coordination chemistry and reactivity of ATIs has been little investigated. We report here Li, Na, and K salts of an ATI ligand with a nitro-substituent in the backbone. It is demonstrated that the NO2 group actively contributes to the coordination chemistry of these complexes, effectively competing with the N,N-binding pocket as a coordination site. This results in an unprecedented E/Z isomerisation of an ATI imino group and culminates in the isolation of the first “naked” (i. e., without directional bonding to a metal atom) ATI anion. Reactions of sodium ATIs with silver(I) and tritylium salts gave the first N,N-coordinated silver ATI complexes and unprecedented backbone substitution reactions. Analytical techniques applied in this work include multinuclear (VT-)NMR spectroscopy, single-crystal X-ray diffraction analysis, and DFT calculations