Transition metal complexes of the PPO/POP ligand: variable coordination chemistry and photo-luminescence properties

Abstract

In the current work the tautomeric equilibrium between tetraphenyldiphosphoxane (Ph₂P–O–PPh₂, POP) and tetraphenyldiphosphine monoxide (Ph₂P–P(O)Ph₂, PPO) in the absence and presence of transition metal precursors is investigated. Whereas with hard transition metal ions, such as Fe(II) and Y(III), PPO-type complexes, such as [FeCl₂(PPO)₂] (1) and [YCl₃(THF)₂(PPO)] (2), are formed, softer transition metals ions tend to form so-called coordination stabilised tautomers of the POP ligand form, such as [Cu₂(MeCN)₃(μ₂-POP)₂](PF₆)₂ (3), [Au₂Cl₂(μ₂-POP)] (4), and [Au₂(μ₂-POP)₂](OTf)₂ (5). The photo-optical properties of the PPO- and POP-type transition metal complexes are investigated experimentally using photo-luminescence spectroscopy, whereby the presence of metallophillic interactions was found to play a crucial role. The dinuclear copper complex [Cu₂(MeCN)₃(μ₂-POP)₂](PF₆)₂ (3) shows a very interesting thermochromic behavior and intense photo-luminescence with remarkable phosphoresence lifetimes at 77 K, which can probably be attributed to short intramolecular Cu–Cu distances.