Abstract
The preparation and characterization of [Cu(POP)(biq)][PF6] and [Cu(xantphos)(biq)][PF6] are reported (biq = 1,1′-biisoquinoline, POP = bis(2-(diphenylphosphanyl)phenyl)ether, and xantphos = (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane). The single crystal structure of [Cu(POP)(biq)][PF6] 0.5Et2O was determined and compared to that in three salts of [Cu(POP)(bq)]+ in which bq = 2,2′-biquinoline. The P–C–P angle is 114.456(19)o in [Cu(POP)(biq)]+ compared to a range of 118.29(3)–119.60(3)o [Cu(POP)(bq)]+. There is a change from an intra-POP PPh2-phenyl/(C6H4)2O-arene π-stacking in [Cu(POP)(biq)]+ to a π-stacking contact between the POP and bq ligands in [Cu(POP)(bq)]+. In solution and at ambient temperatures, the [Cu(POP)(biq)][PF6]+ and [Cu(xantphos)(biq)]+ cations undergo several concurrent dynamic processes, as evidenced in their multinuclear NMR spectra. The photophysical and electrochemical behaviors of the heteroleptic copper (I) complexes were investigated, and the effects of changing from bq to biq are described. Short Cu···O distances within the [Cu(POP)(biq)]+ and [Cu(xantphos)(biq)]+ cations may contribute to their very low photoluminescent quantum yields.
Highlights
Following the seminal studies of McMillin [1,2], heteroleptic copper (I) complexes [Cu(PP)(NN)]+ in which NN is a diimine and PP is a bisphosphane are currently exploited for their emissive [3,4,5,6,7,8] and photocatalytic [9,10,11] properties
Two enantiomers are present in the unit cell with opposite senses of the axial chirality of the chiral axis with one exhibiting (1P) and the other exhibiting (1M) chirality
[Cu(xantphos)(biq)][PF6], which are the first examples of [Cu(P^P)(N^N)]+ complexes in which the N^N ligand is 1,1'-biisoquinoline
Summary
Following the seminal studies of McMillin [1,2], heteroleptic copper (I) complexes [Cu(PP)(NN)]+ in which NN is a diimine and PP is a bisphosphane are currently exploited for their emissive [3,4,5,6,7,8] and photocatalytic [9,10,11] properties. This family of complexes possesses low-lying metal-to-ligand charge transfer (MLCT) excited states, which often exhibit thermally activated delayed fluorescence (TADF) characteristics [8].
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