Luminescent heteroleptic copper(I) complexes with polydentate benzotriazolyl-based ligands

Abstract

Bis(benzotriazol-1-yl)phenylmethane CHPh(btz) 2 and tris(benzotriazol-1-yl)methane CH(btz) 3 were used as N-donor ligands to prepare luminescent heteroleptic copper(I) complexes. [Cu{CHPh(btz) 2 }(PPh 3 ) 2 ][BF 4 ] and [Cu{CHPh(btz) 2 }(DPEphos)] [BF 4 ] (DPEphos = bis[(2-diphenylphosphino)phenyl] ether) were obtained from the corresponding borohydride complexes [Cu(BH 4 )(PPh 3 ) 2 ] and [Cu(BH 4 )(DPEphos)] and tetrafluoroboric acid. [Cu{CH(btz) 3 }(PPh 3 )][BF 4 ] and [Cu{CH(btz) 3 } (P i Pr 3 )][BF 4 ] were prepared from the acetonitrile complex [Cu(NCCH 3 ) 4 ][BF 4 ]. The complexes exhibited bright yellow or orange emissions upon excitation with near-UV and violet light. The photoluminescent properties were attributed to metalto-ligand charge transfer transitions on the basis of experimental data and DFT calculations.

Single-Crystal X-ray Structure Determination of Tris(pyrazol-1-yl)methane Triphenylphosphine Copper(I) Tetrafluoroborate, Hirshfeld Surface Analysis and DFT Calculations

“…The X-ray structures of the hexafluorophosphate and nitrate salts of [Cu(CHpz 3 ) (PPh 3 )] + are, however, present in the Cambridge Crystallographic Data Centre (CCDC 234259 and 246420) [27,28]. The related [Cu(CHbtz 3 )(PPh 3 )][BF 4 ] complex, where CHbtz 3 is tris(benzotriazol-1-yl)methane, was recently reported by our research group together with the single-crystal X-ray structure determination of CHbtz 3 [29]. Given our interest towards the preparation of Cu(I) coordination compounds with polydentate azole-based ligands [30,31], in this paper, we report the synthesis, characterization and single-crystal X-ray structure determination of [Cu(CHpz 3 )(PPh 3 )][ BF 4 ].…”

Substituted Pyrrole‐based Schiff Bases: Effect On The Luminescence Of Neutral Heteroleptic Cu(I) Complexes

“…[21][22][23][24][25][26] Hence, neutral Schiff bases were successfully employed for the preparation of photoactive cationic Cu(I) complexes. [27][28][29] Given our interest in luminescent Cu(I) derivatives, [30][31][32][33][34][35][36][37] we deemed it interesting to investigate the effect of substituted pyrrole-based Schiff bases in the photophysical properties of the derived complexes. The use of imines as chelating N-donors for Cu(I) was previously described by Eisenberg's group.…”

“…Given our interest in luminescent Cu(I) derivatives, [30–37] we deemed it interesting to investigate the effect of substituted pyrrole‐based Schiff bases in the photophysical properties of the derived complexes. The use of imines as chelating N‐donors for Cu(I) was previously described by Eisenberg's group [38] .…”

Visible-emitting Cu(i) complexes with N-functionalized benzotriazole-based ligands

“…[55][56][57] Our research group recently exploited benzotriazole and the related heterocycle indazole as coordinating moieties in polydentate ligands applied for the preparation of luminescent Cu(I) complexes. [58][59][60] So far, the conjugation of benzotriazole in combination with a different aromatic N-donor heterocycle was not considered. Herein we report the synthesis and characterization of bright yellow-and reddish orange-emitting Cu(I) complexes with bidentate ligands obtained by functionalization of the benzotriazole NH moiety with other heterocycles, in particular pyridine, pyrimidine and alkoxy-substituted triazines.…”

“…55–57 Our research group recently exploited benzotriazole and the related heterocycle indazole as coordinating moieties in polydentate ligands applied for the preparation of luminescent Cu( i ) complexes. 58–60…”