Designing luminescent diimine-Cu(i)–phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra

Abstract

Herein, six new [Cu(N^N)(P^P)]+/0 complexes with different N-ligand and counteranions [Cu2(dmp)2(bdppmapy)I2] (1), [Cu2(dmp)2(bdppmapy)(CN)2]·3CH3OH (2), [Cu(dmp)(bdppmapy)](BF4) (3), [Cu(dmp)(bdppmapy)](ClO4) (4), [Cu(phen)(bdppmapy)](BF4) (5), [Cu(phen)(bdppmapy)](ClO4) (6) have been synthesized and characterized (bdppmapy = N,N-bis[(diphenylphosphino)methyl]-2-pyridinamine,...

Study on the luminescence properties of ionic [Cu(N^N)(P^P)]+ complexes: influence of ligands, counteranions and weak interactions

“…There is an obvious absorption peak at 1.2–1.6 THz in the THz absorption spectra of the phen series complexes 1a–4a , consistent with the previous studies, which is related to the C–H⋯π interactions in the complexes. 49,56–58 The Dpq series complexes 3b and 4b with C–H⋯π interactions show obvious absorption peaks near 1.2–1.6 THz. Due to the absence of π–π and C–H⋯π interactions in complexes 1b and 2b , there is almost no absorption in the corresponding low frequency range of the THz spectra and the absorption peak begins to appear after 2.0 THz.…”

Multistimuli-responsive multicolor solid-state luminescence tuned by NH-dependent switchable hydrogen bonds

“…For Cu( i )-diimine-diphosphine systems, it has been shown that the highest occupied molecular orbital (HOMO) is mainly composed of Cu( i ) and P atoms, and the lowest unoccupied molecular orbital (LUMO) is basically centered on diimine. 26–33 The selection of diimine and diphosphine ligands is thus crucial to the accurate synthesis of stimuli-responsive luminescent materials of such Cu( i ) complexes. Both bis(diphenylphosphine) amine (dppa) and 5- tert -butyl-3-(2′-pyrimidinyl)-1 H -1,2,4-triazole (bpmtzH) feature an N–H functional group that readily yields hydrogen bonding with neighbouring solvent molecules and counter-ions.…”