In the current work the tautomeric equilibrium between tetraphenyldiphosphoxane (Ph2P-O-PPh2, POP) and tetraphenyldiphosphine monoxide (Ph2P-P(=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 [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 [Cu-2(MeCN)(3)(mu(2)-POP)(2)](PF6)(2) (3), [Au2Cl2(mu(2)-POP)] (4), and [Au-2(mu(2)-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 [Cu-2(MeCN)(3)(mu(2)-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.
Transition metal complexes of the PPO/POP ligand: variable coordination chemistry and photo-luminescence properties / F. Flecken, T. Grell, S. Hanf. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - 51:23(2022 Jun 13), pp. 8975-8985. [10.1039/D2DT01091G]
Transition metal complexes of the PPO/POP ligand: variable coordination chemistry and photo-luminescence properties
T. GrellSecondo
;
2022
Abstract
In the current work the tautomeric equilibrium between tetraphenyldiphosphoxane (Ph2P-O-PPh2, POP) and tetraphenyldiphosphine monoxide (Ph2P-P(=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 [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 [Cu-2(MeCN)(3)(mu(2)-POP)(2)](PF6)(2) (3), [Au2Cl2(mu(2)-POP)] (4), and [Au-2(mu(2)-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 [Cu-2(MeCN)(3)(mu(2)-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.File | Dimensione | Formato | |
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