Synthesis and Structural Characterization of Cu(I) and Ni(II) Complexes that Contain the Bis[2-(diphenylphosphino)phenyl]ether Ligand. Novel Emission Properties for the Cu(I) Species

Abstract

The pseudotetrahedral complexes [Cu(NN)(DPEphos)]BF(4), where DPEphos = bis[2-(diphenylphosphino)phenyl]ether and NN = 1,10-phenanthroline (1), 2,9-dimethyl-1,10-phenanthroline (2), 2,9-di-n-butylphenanthroline (3), or two dimethylcyanamides (4), and NiCl(2)(DPEphos) (5) have been synthesized and structurally characterized by X-ray crystallography and their solution properties examined by use of a combination of cyclic voltammetry, NMR spectroscopy, and electronic absorption spectroscopy. Complexes 1-4 possess a reversible Cu(II)/Cu(I) couple at potentials upward of +1.2 V versus Ag/AgCl. Compounds 1-3 exhibit extraordinary photophysical properties. In room-temperature dichloromethane solution, the charge-transfer excited state of the dmp (dbp) derivative exhibits an emission quantum yield of 0.15 (0.16) and an excited-state lifetime of 14.3 mus (16.1 mus). Coordinating solvents quench the charge-transfer emission to a degree, but the photoexcited dmp complex 2 retains a lifetime of over a microsecond in acetone, methanol, and acetonitrile.

Stimuli-responsive Luminescent Copper(I) Complexes for Intelligent Emissive Devices

“…The thermochromic luminescence of 13 is reported to originate from the 3 CC emission with the shrinkable tetranuclear cubane-type core, whereas the less pronounced temperature dependent emission of 14 is derived from the 3 XLCT excited state. By using mechanochemical method, we have succeeded in the preparation of luminescent mononuclear copper complexes, (15), iq (16), nap (17): py: pyridine; iq: isoquinoline; nap: 1,6-naphthyridine). 49 It should be noteworthy that the mechanochemical syntheses of these complexes were achieved without the use of any assisting solvent; the mixture of CuI, PPh 3 , and the corresponding ligand L (molar ratio of 1:2:3, respectively) were ground with a pestle in an agate mortar to form complexes 16 and 17 within a few minutes (Figure 12).…”

Copper(I) Complexes of Bis(2-(diphenylphosphino)phenyl) Ether: Synthesis, Reactivity, and Theoretical Calculations

“…(2.2614(9), 2.2712(7) Å) (NN = 2,9-dimethyl-1,10-phenanthroline or 2,9-di-n-butyl-1,10-phenanthroline). 5 The geometry around copper in complex 2 is pseudo-tetrahedral. The Cu1-P4, (BozPHOS = 1,2-Bis(2,5-dimethylphospholano)benzene mono-oxide).…”

“…[1][2][3][4] In recent years, there has been several reports on mixed ligand complexes containing both bis(phosphines) and polypyridyls. 5,6 These complexes have been easily synthesized by treating bis(phosphines) with appropriate metal precursors followed by the addition of N-donor ligands. The mixed ligand systems consisting of both bis(phosphines) and partially functionalized or oxidized ligands are less extensive.…”

Crystal structure of μ-1,4-bis(diphenylphosphine)butane-2,9-dimethyl-1,10-phenanthroline-κ2 N:N′-bis(cyano-κC)dicopper(I)]-water, C58H56Cu2N6O2P2

“…The coordination geometry around each Cu atom indicates a distorted tetrahedron. The N-Cu-N bond angle (79.13 (12) (dmp = 2,9-dimethyl-1,10-phenanthroline DPEphos = bis[2-(diphenylphosphino)phenyl]-ether) [11]. The Cu-C bond distance 1.919(4) Å in the title complex is longer than that observed in [Cu(dmp)(CN)] (1.897(1) Å) [9].…”