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(![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
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.
- This article is part of the themed collections: Dalton Transactions up-and-coming articles and Open Access in Dalton Transactions
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