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Homometallic bi- and trinuclear complexes of Cu, Ag and Au ligated by a tetradentate PNNP ligand are shown. Photoluminescence and theoretical studies revealed a MLCT character upon UV excitation and complemented this work.

Tetranuclear homo- and heterometallic coinage metal complexes, as well as a hexanuclear gold complex, were synthesized. All feature a metal string structure.

Heterometallic complexes, combining metals of the outer rims of the d-block, for example lanthanides(III) (Ln) and coinage metals(I) (M) are scarcely reported, synthetically challenging and highly interesting in terms of their interactions. In this context, we synthesized hetero-bimetallic LnÀ M compounds ligated by the phosphine functionalized amidinate system (N,N'-bis[(2-diphenylphosphino)phenyl] formamidinate, "dpfam"). The resulting compounds [dpfam 3 LnM][OTf] (Ln = La, Nd and M = Ag, Au) feature a close proximity of the two metal centres and were investigated experimentally by photoluminescence spectroscopy and quantum chemical calculations. The latter showed rare LaÀ Au interactions for the first excited state.

Combining phase-dependent photoluminescence (PL) measurements and quantum chemical calculations is ap owerful approacht oh elp understand the influence of the molecular surroundings on the PL properties.Herein, aphosphine functionalized amidinate was used to synthesize ar ecently presented bimetallic gold complex, featuring an unusual charge separation. The latter was subsequently used as metalloligand to yield heterotetrametallic complexes with an Au-M-M-Au "molecular wire" arrangement (M = Cu, Ag,Au) featuring metallophilic interactions.A ll compounds showb right phosphorescence in the solid state,also at ambient temperature.The effect of the molecular environment on the PL was studied in detail for these tetrametallic complexes by comparative measurements in solution, in the solid state and in the gas phase and contrasted to time-dependent density functional theory computations.

Solvation of [(CNT)Ln(η8‐COT)] (Ln=La, Ce, Nd, Tb, Er; CNT=cyclononatetraenyl, i.e., C9H9−; COT=cyclooctatetraendiid, i.e., C8H82−) complexes with tetrahydrofuran (THF) gives rise to neutral [(η4‐CNT)Ln(thf)2(η8‐COT)] (Ln=La, Ce) and ionic [Ln(thf)x(η8‐COT)][CNT] (x=4 (Ce, Nd, Tb), 3 (Er)) species in a solid‐to‐solid transformation. Due to the severe distortion of the ligand sphere upon solvation, these species act as switchable luminophores and single‐molecule magnets. The desolvation of the coordinated solvents can be triggered by applying a dynamic vacuum, as well as a temperature gradient stimulus. Raman spectroscopic investigations revealed fast and fully reversible solvation and desolvation processes. Moreover, we also show that a Nd:YAG laser can induce the necessary temperature gradient for a self‐sufficient switching process of the Ce(III) analogue in a spatially resolved manner.

No abstract

Solvation of [(CNT)Ln(η8‐COT)] (Ln=La, Ce, Nd, Tb, Er; CNT=cyclononatetraenyl, i.e., C9H9−; COT=cyclooctatetraendiid, i.e., C8H82−) complexes with tetrahydrofuran (THF) gives rise to neutral [(η4‐CNT)Ln(thf)2(η8‐COT)] (Ln=La, Ce) and ionic [Ln(thf)x(η8‐COT)][CNT] (x=4 (Ce, Nd, Tb), 3 (Er)) species in a solid‐to‐solid transformation. Due to the severe distortion of the ligand sphere upon solvation, these species act as switchable luminophores and single‐molecule magnets. The desolvation of the coordinated solvents can be triggered by applying a dynamic vacuum, as well as a temperature gradient stimulus. Raman spectroscopic investigations revealed fast and fully reversible solvation and desolvation processes. Moreover, we also show that a Nd:YAG laser can induce the necessary temperature gradient for a self‐sufficient switching process of the Ce(III) analogue in a spatially resolved manner.