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. Grell
Secondo
;
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.
Settore CHIM/03 - Chimica Generale e Inorganica
13-mag-2022
Article (author)
File in questo prodotto:
File Dimensione Formato  
d2dt01091g.pdf

accesso aperto

Tipologia: Publisher's version/PDF
Dimensione 1.69 MB
Formato Adobe PDF
1.69 MB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/933151
Citazioni
  • ???jsp.display-item.citation.pmc??? 0
  • Scopus 0
  • ???jsp.display-item.citation.isi??? 0
social impact