Platinum(II) Complexes with 10-(Aryl)phenoxarsines: Synthesis, Cis/Trans Isomerization, and Luminescence

Abstract

Synthesis and structural and photophysical characterization of platinum dihalogenide complexes formulated as [PtHal2L2], where Hal = Cl and I, with different 10-(aryl)­phenoxarsine ligands such as 10-(p-chlorophenyl)­phenoxarsine, 10-(p-tolyl)­phenoxarsine, and 10-(phenyl)­phenoxarsine are reported. The structures of complexes were determined by NMR spectroscopy, mass spectrometry, and X-ray analysis. Cis/trans isomerism of the complexes in solution was studied by NMR spectroscopy. In the solid state, under UV irradiation, platinum diiodide trans complexes exhibit an intense orange-red emission, which was attributed to a metal halide-centered triplet state. The UV/vis absorption and emission properties were studied and rationalized by density functional theory (DFT) and time-dependent DFT calculations.

Emission Properties of Eu(III) Complexes Containing Arsine and Phosphine Ligands with Annulated Structures

“…The solvents were removed in vacuo, and the residue was subjected to recrystallization (slow evaporation from solution of the product in mixture of CH 2 Cl 2 and MeOH at ambient temperature) to obtain the titled product as a colorless solid (34%, 277 mg, 0.867 mmol). The chemical structure was confirmed in reference to a previous report …”

“…The chemical structure was confirmed in reference to a previous report. 29 9-Phenyl-9-arsafluorene Oxide (1). A THF (36 mL) solution of 5phenyldibenzarsole (533 mg, 1.75 mmol) and H 2 O 2 (30%, 1.01 g) was stirred for 13 h under ambient conditions.…”

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

“…The empty NTO in the dominant pair is a mixture of a 5 d (Pt) orbital with a 6 p (I) and 4 s ,4 p (As) orbitals. In contrast, the occupied NTO in the pair is comprised of π‐ligand‐based orbitals (LUMO) [74] …”

“…The platinum(II) complexes of 10-(pchlorophenyl)phenoxarsine ( 27), 10-(p-tolyl)phenoxarsine ( 28), and 10-(phenyl)phenoxarsine (29) were synthesized, and their photophysical properties were studied. [74] The halide ligand seems to have a substantial impact on their coordination behaviour, as the reactions of 10-(aryl)phenoxarsines (L = 27-29) with Pt(COD)Cl 2 (COD = 1,5-cyclooctadiene) in 2 : 1 molar ratio in dichloromethane afforded cis-PtCl 2 (L) 2 complexes which upon reaction with KI converted to trans-PtI 2 (L) 2 complexes (Scheme 5). All of these complexes have been fully characterized by various spectroscopic methods.…”

Diastereomeric dinickel(ii) complexes with non-innocent bis(octaazamacrocyclic) ligands: isomerization, spectroelectrochemistry, DFT calculations and use in catalytic oxidation of cyclohexane

“…Geometrical isomerization in mononuclear Werner-type metal complexes is a well-documented transformation, 58,59 which can be also induced by electron transfer. [60][61][62] During the preparation of pyridyl-bearing compound 5, we observed that the ratio of the anti-and syn-isomers changed over several weeks at room temperature with a preference for the synisomer formation.…”