Manipulating crystallization dynamics through chelating molecules for bright perovskite emitters

Molecular additives are widely utilized to minimize non-radiative recombination in metal halide perovskite emitters due to their passivation effects from chemical bonds with ionic defects. However, a general and puzzling observation that can hardly be rationalized by passivation alone is that most of the molecular additives enabling high-efficiency perovskite light-emitting diodes (PeLEDs) are chelating (multidentate) molecules, while their respective monodentate counterparts receive limited attention. Here, we reveal the largely ignored yet critical role of the chelate effect on governing crystallization dynamics of perovskite emitters and mitigating trap-mediated non-radiative losses. Specifically, we discover that the chelate effect enhances lead-additive coordination affinity, enabling the formation of thermodynamically stable intermediate phases and inhibiting halide coordination-driven perovskite nucleation. The retarded perovskite nucleation and crystal growth are key to high crystal quality and thus efficient electroluminescence. Our work elucidates the full effects of molecular additives on PeLEDs by uncovering the chelate effect as an important feature within perovskite crystallization. As such, we open new prospects for the rationalized screening of highly effective molecular additives.

Mixed Ligand Complexes of Transition Metal Ions with Selective Bio-Ligands in Surfactant-Water Mixtures

Chemical speciation of ternary complexes of L-arginine and L-aspartic acid with essential transition metal ions was studied pH metrically. The following MLX, MLXH and ML2X ternary species are detected and reported in this paper. The existence of different ternary species is established from modeling studies using the computer program MINIQUAD75. The relative concentrations (M: L: X=1:2:2, 1:2:4, 1:4:2) and stabilities of the ternary species are compared with those of binary species. The extra stability associated with the ternary complexes is attributed to factors such as charge neutralization, chelate effect, stacking interactions and hydrogen bonding. Trend in variation of stability constants with the change in the mole fraction of the surfactant in various micellar media is explained on the basis of electrostatic and non-electrostatic forces. Distribution diagrams in relation to pH and plausible structures were presented.

Synthesis, Identification of Co(II), Cu(II) and Ni(II) Complexes with A Schiff Base–Azo Ligand Derived from Imidazol Derivatives, 4- Aminoacetophenon and 4- Chloroaniline and Study Their Physical Properties and Their Thermodynamic Stabilities

The complexes of Co(II), Cu(II) and Ni(II) were synthesized by using schiff base – azo as a ligand, which were prepared under this study by the reaction between the Schiff base diazonium salt and the imidazole derevitive. They were characterized by element analysis, FTIR spectroscopy and UV.VIS. spectroscopy. Their electric conductivity and magnetic features were determined. Their stepwise and overall stability constants and their thermodynamic data ( , and ) were determined. The results showed that all the complexes have paramagnetic features and all of them have good conductivity. The formula of the complexes under this paper were suggested by using the mole ratio method which lead to the formation of (1 : 2) metal : ligand formula for all the complexes. In all the complexes the coordinated sites was through N atoms of the azo groups and N atom of the imidazol ring. The suggested geometrical shapes of the complexes was the octahedral shape due to the ( d2sp3 ) hybridization. Their stepwise stability constants were determined, it was found that for all the complexes they were increased toward the addition of ligand that because of the chelate effect. Their overall stability constants were determined, it was found that for all the complexes were high that because of the chelate effect. Their thermodynamic functions ( , and ) were had negative value, that refer to good stability for the complexes and these results were satisfied with the spontaneous reaction and high stability complexes.

N-Heterocyclic Carbene Adducts of Alkynyl Functionalized 1,3,2-Dithioborolanes

Alkynyl functionalized boron compounds are versatile intermediates in the areas of medicinal chemistry, materials science, and optical materials. In particular, alkynyl boronate esters [R1−C≡C−B(OR2)2] are of interest since they provide reactivity at both the alkyne entity, with retention of the B−C bond or alkyne transfer to electrophilic substrates with scission of the latter. The boron atom is commonly well stabilized due to (i) the extraordinary strength of two B−O bonds, and (ii) the chelate effect exerted by a bifunctional alcohol. We reasoned that the replacement of a B−O for a B−S bond would lead to higher reactivity and post-functionalization in the resulting alkynyl boronate thioesters [R1−C≡C−B(S2X)]. Access to this poorly investigated class of compounds starts form chloro dithioborolane cyclo-Cl−B(S2C2H4) as a representative example. Whereas syntheses of three coordinate alkynyl boronate thioesters [R1−C≡C−B(S2X)] proved to be ineffective, the reactions of NHC-adducts (NHC = N-heterocyclic carbene) of cyclo-Cl-B(S2C2H4) afforded the alkyne substituted thioboronate esters in good yield. The products NHC−B(S2C2H4)(C≡C-R1) are remarkably stable towards water and air, which suggests their use as boron-based building blocks for applications akin to oxygen-based boronate esters.