Multi-Mode Switchable Luminescence of Tetranuclear Cubic Copper(I) Iodide Complexes with Tertiary Arsine Ligands

Abstract

Tetranuclear cubic copper(I) iodide (CuI) complexes were synthesized by utilizing tertiary arsine ligands such as triphenylarsine, tri(p-tolyl)arsine, 9-phenyl-9-arsafluorene, and 1-phenylarsolane; except for triphenylarsine, these ligands were prepared by the practical methods that we previously developed. The obtained complexes exhibited intense emission in the crystalline states even at room temperature. Their emission colors were drastically changed by mechanical stimulus, temperature, and excitation wavelength. These complexes are the first examples of cubic Cu4I4 complexes with arsenic ligands exhibiting stimuli-responsive and excitation wavelength-dependent luminescence.

Design of luminescent complexes with different Cu4I4 cores based on pyridyl phenoxarsines

“…† The Cu 4 I 4 core of 7a is asymmetrically distorted (the intramolecular Cu-Cu distances are 2.666, 2.676, 2.692, 2.711, 2.732, and 2.816 Å). These values are comparable to the corresponding values for cubanes with 10-(R-phenyl) phenoxarsines, 20 N-methyl-10-( p-halogenophenyl)-5,10-dihydrophenarsazines, 11 AsEt 3 , 53 AsPh 3 , 12 As( p-Tol) 3 , 12 9-phenyl-9arsafluorene, 12 and 1-phenylarsolane 12 and are shorter than those found in complexes based on phosphine ligands. 14,17,18,[55][56][57] Fig.…”

“…1,2,8 A wide range of monodentate pnictogen ligands (N, P, As, Sb) are used as a platform for supporting the cubane Cu 4 I 4 core. [9][10][11][12][13][14][15][16][17][18][19][20] Stair-step motifs are usually supported by bidentate (e.g. N^N-, [21][22][23] P^P-, 24 P^N-bidentate [25][26][27][28] ) and N^N^N-tridentate ligands, [29][30][31][32][33] while examples based on monodentate ligands are less common.…”

Robust and highly emissive copper(i) halide 1D-coordination polymers with triphenylarsine and a series of bridging N-heteroaromatic co-ligands

“…1a and b). 9 The emission properties of the complexes with AsPh 3 are stimuli-sensitive. Mechanical stimuli, such as grinding in a mortar, can easily change the emission color.…”

Copper(I)‐Arsine Clusters with a Near‐Unity Phosphorescence Quantum Yield for X‐Ray Scintillation and LED Applications

“…As seen from Figure 1b, X-Ray structures of 1-4 reveal a general Cu 4 I 4 unit adopting a typical cubane-like structure found in [Cu 4 I 4 L 4 ] clusters. [20,47] The Cu•••Cu contacts of 1-4 being ≈2.70-2.95 (cf. twice van der Waals radius of Cu, 2.80 Å [55] ) imply metalophilic interactions, which are quite specific for Cu 4 I 4 clusters.…”

“…Potentially, arsine/stibine ligands can also improve X-ray scintillation efficiency of the Cu 4 I 4 clusters through higher X-ray absorption ability of As/Sb nuclei compared to N, P, or S nuclei. However, despite the recent progress in studying Cu(I)-arsine emitters by Naka, [47][48][49] Karasik, [50,51] and our groups, [46,[52][53][54] these compounds still remain poorly explored. In particular, they have never been demonstrated in X-ray scintillation or white light LED (WLED) applications.…”