Transition metal complexes of the PPO/POP ligand: variable coordination chemistry and photo-luminescence properties
| Autor: | Franziska Flecken, Toni Grell, Schirin Hanf |
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| Jazyk: | angličtina |
| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Dalton transactions (Cambridge, England : 2003), 51 (23), 8975–8985 |
| ISSN: | 1477-9234 0300-9246 1470-479X 1477-9226 2050-5671 |
| DOI: | 10.5445/ir/1000148199 |
| Popis: | In the current work the tautomeric equilibrium between tetraphenyldiphosphoxane (Ph$_2$P–O–PPh$_2$, POP) and tetraphenyldiphosphine monoxide (Ph$_2$P–P([double bond, length as m-dash]O)Ph$_2$, 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 [FeCl$_2$(PPO)$_2$] and [YCl$_3$(THF)$_2$(PPO)], are formed, softer transition metals ions tend to form so-called coordination stabilised tautomers of the POP ligand form, such as [Cu$_2$(MeCN)$_3$(μ$_2$-POP)$_2$](PF$_6$)$_2$, [Au$_2$Cl$_2$(μ$_2$-POP)], and [Au$_2$(μ$_2$-POP)$_2$](OTf)$_2$. 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 [Cu$_2$(MeCN)$_3$(μ$_2$-POP)$_2$](PF$_6$)$_2$ 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. |
| Databáze: | OpenAIRE |
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