Synthesis, structure, and luminescence of the “octahedral” cluster Cu4I4(rac-IsMePCH2PMeIs)2 (Is=2,4,6-(i-Pr)3C6H2)

Synthesis, X‐ray Structures, and Photoluminescence of the Octahedral Cu4I4 Cluster with Bulky Bidentate Bis(phosphanyl)amine Ligand

“…The Cu I –Cu I bond lengths are comparable with those found in analogous complexes reported in the literature , , . The Cu I –I bond lengths involved in the μ 4 ‐bridging [2.7034(13)–2.9382313) Å] are significantly longer than those participating in μ 2 ‐bridging [2.5994(11) and 2.6398(12) Å] and are comparable to those found in analogous Cu 4 I 4 core reported in the literature , . The P–N–P bond angle [117.4(3)°] is shorter than P–N–P bond angles [120.1(3) and 120.83(12)°] found in [Cu 4 I 4 {C 6 H 5 N(PR 2 ) 2 } 2 ] [R = OC 6 H 4 (OMe‐ o )(C 3 H 5 ‐ p ) and R = OC 6 H 4 (C 3 H 5 ‐ o )] .…”

“…The bidentate ligands are generally required to obtain the square or rectangular Cu 4 plane with two axial μ 4 ‐iodides, and two μ 2 ‐iodides. To the best of our knowledge, there are a limited examples of structurally characterized octahedral Cu 4 I 4 clusters of bidentate P,P ‐ and P,N ‐ chelating ligands . As with the cubane analogues, emission in these clusters has been showed temperature dependent emission from 3 XLCT (halide‐to‐ligand charge transfer) and 3 CC (Cu 4 I 4 cluster‐centered) triplet excited states.…”

Tuning the architectures and luminescence properties of Cu(i) compounds of phenyl and carboranyl pyrazoles: the impact of 2D versus 3D aromatic moieties in the ligand backbone

“…The geometric parameters have been compared with other reported examples. There are only fifteen entries in the CSD 95 for eleven such type of octahedral cluster compounds and all of them bear two bidentate (neutral P^N 25,31,96,97 or anionic N^N 19 ) ligands. Thus, complex 3 represents the first example of such a family having monosubstituted neutral N-donor ligands.…”

“…25 Regarding octahedral compounds, reports including photophysical studies are much scarcer, with fewer than a dozen papers published on the subject. 19,23,[25][26][27][28][29][30][31] This can be attributed to the fact that octahedral cores are energetically unfavourable compared to the cubane cores, as demonstrated by theoretical calculations. 28 Optical properties of these octahedral compounds have also been studied and various reports suggest that the rigidity and steric demands of the ligands seems to play a more significant role in the photophysical properties than in the cubane type clusters.…”

“…4,5,18,32 Structures with N-ligands (either monodentate or multidentate) are by far more common and show intriguing luminescent properties. 25,33 Reported examples on octahedral motifs include bidentate ligands bearing small angles (e.g., P^N, 23,25,27,28,30 P^P, 26,29,31,[34][35][36][37] C^P 38 and N^N 19 ), with only one example based on a monodentate N-heterocyclic carbene ligand. 39 Within the family of polynuclear Cu(I) compounds containing N-ligands, pyrazoles are significantly less studied than the overwhelming family of pyridines.…”