Jana Schiller

Bio: Jana Schiller is an academic researcher. The author has contributed to research in topics: Bipyridine & Ligand. The author has an hindex of 1, co-authored 1 publications receiving 3 citations.

Self-assembled luminescent Cu(I) tetranuclear metallacycles based on 3,3′-bipyridine ligands

Abstract: 3,3'-Bipyridine ligand B was reacted with pre-assembled [Cu-2(mu(2)-dppm)(2)] Cu(I) bimetallic flexible precursor A according to coordination-driven supramolecular chemistry synthetic principles. Outcomes obtained revealed the necessity to formally introduce bridging halide X ions (X = Cl, Br or I) in order to conduct selectively and successfully coordination-driven supramolecular syntheses. Therefore, [Cu-2(mu(2)-dppm)(2)(mu(2)-X)] bimetallic connecting nodes presenting a potential coordination angle of ca. 120 degrees are generated, which lead upon reaction with connecting ligand B to the selective formation of new tetranuclear metallacycles C-X. These derivatives are luminescent in the solid-state at room temperature with high emission quantum yields and a study of the temperature dependence of their photophysical properties was conducted, suggesting a ligand B centered triplet origin for their luminescence.

Pyridylarsine-based Cu(<scp>i</scp>) complexes showing TADF mixed with fast phosphorescence: a speeding-up emission rate using arsine ligands

Abstract: Can arsine ligands be preferred over similar phosphines to design Cu(I)-based TADF materials? The present study reveals that arsines can indeed be superior to reach shorter decay times of Cu(I) emitters. This has been exemplified on a series of bis(2-pyridyl)phenylarsine-based complexes [Cu2(Py2AsPh)2X2] (X = Cl, Br, and I), the emission decay times of which are significantly shorter (2-9 μs at 300 K) than those of their phosphine analogs [Cu2(Py2PPh)2X2] (5-33 μs). This effect is caused by two factors: (i) large ΔE(S1-T1) gaps of the arsine complexes (1100-1345 cm-1), thereby phosphorescence is admixed with TADF at 300 K, thus reducing the total emission decay time compared to the TADF-only process by 5-28%; (ii) higher SOC strength of arsenic (ζl = 1202 cm-1) against phosphorus (ζl = 230 cm-1) makes the kr(T1 → S0) rate of the Cu(I)-arsine complexes by 1.3 to 4.2 times faster than that of their phosphine analogs. It is also noteworthy that the TADF/phosphorescence ratio for [Cu2(Py2AsPh)2X2] at 300 K is halogen-regulated and varies in the order: Cl (1 : 1) < Br (3 : 1) ≈ I (3.5 : 1). These findings provide a new insight into the future design of dual-mode (TADF + phosphorescence) emissive materials with reduced lifetimes.

Tris(2-Pyridyl)Arsine as a New Platform for Design of Luminescent Cu(I) and Ag(I) Complexes

Abstract: The coordination behavior of tris(2-pyridyl)arsine (Py3As) has been studied for the first time on the example of the reactions with CuI, CuBr and AgClO4. When treated with CuI in CH2Cl2 medium, Py3As unexpectedly affords the scorpionate complex [Cu(Py3As)I]∙CH2Cl2 only, while this reaction in MeCN selectively leads to the dimer [Cu2(Py3As)2I2]. At the same time, the interaction of CuBr with Py3As exclusively gives the dimer [Cu2(Py3As)2Br2]. It is interesting to note that the scorpionate [Cu(Py3As)I]∙CH2Cl2, upon fuming with a MeCN vapor (r.t., 1 h), undergoes quantitative dimerization into the dimer [Cu2(Py3As)2I2]. The reaction of Py3As with AgClO4 produces complex [Ag@Ag4(Py3As)4](CIO4)5 featuring a Ag-centered Ag4 tetrahedral kernel. At ambient temperature, the obtained Cu(I) complexes exhibit an unusually short-lived photoluminescence, which can be tentatively assigned to the thermally activated delayed fluorescence of (M + X) LCT type (M = Cu, L = Py3As; X = halogen). For the title Ag(I) complexes, QTAIM calculations reveal the pronounced argentophilic interactions for all short Ag∙∙∙Ag contacts (3.209–3.313 Å).

Structure characterization and luminescent properties of trigonal Cu(I) iodine/bromine complexes comprising cation–π interactions

Abstract: Three-coordinate mononuclear copper(I) halide complexes (1 (I) and 2 (Br)), which bear a novel rigid diphosphine ligand derived from a benzimidazole skeleton, were prepared and characterized. Structural analyses of 1...