Structures, electronic properties and solid state luminescence of Cu(i) iodide complexes with 2,9-dimethyl-1,10-phenanthroline and aliphatic aminomethylphosphines or triphenylphosphine

Abstract

The luminescent complexes of triphenylphosphine and two interesting aminomethylphosphines: P(CH(2)N(CH(2)CH(2))(2)NCH(3))(3) and P(CH(2)N(CH(2)CH(2))(2)O)(3) with copper(I) iodide and 2,9-dimethyl-1,10-phenanthroline (dmp): [CuI(dmp)PPh(3)], [CuI(dmp)P(CH(2)N(CH(2)CH(2))(2)NCH(3))(3)] and [CuI(phen)P(CH(2)N(CH(2)CH(2))(2)O)(3)] are presented in this work. These complexes were characterized in solution by means of NMR spectroscopy and their structures were crystallographically determined in the solid state. All complexes crystallize as the discrete dimers bound by π-stacking interactions between dmp rings. The coordination geometry about the Cu(I) centre is pseudo-tetrahedral showing small flattening and large rocking distortions. The investigated compounds exhibit intense orange photoluminescence in the solid state (emission peaks at r.t.: λ(max) = 588-592 nm; τ = 1.7-2.2 and 6.4-10.0 μs; at 77 K: λ(max) = 605-612 nm; τ = 4.8-6.5 and 32-47 μs), which is several orders higher than the luminescence of the analogous complexes with 1,10-phenanthroline (phen). Electronic and structural properties of the [CuI(dmp/phen)PR(3)] complexes were characterized using DFT methods to interpret their photophysics. On the basis of TDDFT calculations the broad CT bands observed in UV-Vis spectra are interpreted as the two mixed transitions from σ(CuI) bond with a small admixture of σ(CuP) bond to π* phen or dmp ligand: (MX,MPR(3))LCT, while the emissions most probably occur from two triplet states which are in thermal equilibrium.

Biological activity and structure dependent properties of cuprous iodide complexes with phenanthrolines and water soluble tris (aminomethyl) phosphanes

“…The geometry of 3P obtained with DFT methods slightly differs from the X-ray structure. As in the case of other Cu(I) complexes systematic elongation of the bonds is most noticeable [30], however the S4 parameter for 3P (43.73) is in a good agreement with S4′ from the X-ray structure. The value od the S4 parameter for 3P is significantly smaller than S4 values estimated for 1P (48.26) and 2P (49.61), which perfectly reflects the differences in S4′ parameters.…”

“…The lengths of the Cu\I and Cu\P bonds in 3P (Table 1) are in a typical range, however the I\Cu\P bond angle (104.79(2)°) is one of the smallest among the similar complexes [5,30,48,49]. The value of the S4′ parameter for the phosphane 3 in the studied crystal (46.3) is significantly smaller than the S4′ values for 1 in 1P (50.8 and 49.7) and 2 in 2P (50.7) [30]. This indicates greater changes in electron density distribution around phosphorus atom caused by the formation of the P\Cu bond and, indirectly, by a stronger coordination of 3 in the complex in comparison with to 1 or 2.…”

“…2) for this compound. This parameter is a good indicator for the changes in the electron distribution in the phosphorus atom [30,40] during the coordination or chalcogenide formation processes. The S4 value for 3 (63.39) was close to the value calculated for 2 (63.40) and slightly smaller than the value for 1 (63.70).…”

X-ray absorption spectroscopy: towards more reliable models in material sciences

“…In fact, even after isolation and in the solid state, some Cu(I) complexes undergo dissociation and rearrangement reactions, as it has been investigated for various examples of cationic complexes. [28,[32][33][34][35][36][37][38][39] This is why the possibility of deviations from models based on single crystal X-ray diffraction in real, amorphous samples needs to be taken into account. X-ray absorption spectroscopy offers the possibility to do this, as will be demonstrated in the next sections.…”

Copper(I) (Pseudo)Halide Complexes with Neocuproine and Aminomethylphosphines Derived from Morpholine and Thiomorpholine – In Vitro Cytotoxic and Antimicrobial Activity and the Interactions with DNA and Serum Albumins

“…This work is a part of our ongoing studies on tris(aminomethyl)phosphines and their complexes with copper(I) iodide or isothiocyanate and diimines . Our previously obtained results indicate that the copper(I) iodide complexes with tris(aminomethyl)phosphines and with 2,9‐dimethyl‐1,10‐phenanthroline (dmp) ligand showed much higher antimicrobial activity than the ones with 1,10‐phenanthroline (phen) or 2,2′‐biquinoline (bq) .…”