Bright Phosphorescence of a Trinuclear Copper(I) Complex:  Luminescence Thermochromism, Solvatochromism, and “Concentration Luminochromism”

Abstract

A photophysical study is reported for the trinuclear copper(I) complex {[3,5-(CF3)2Pz]Cu}3. The neutral compound exhibits multicolor bright phosphorescent emissions both in the solid state and in solution. The emission can be tuned to multiple visible colors by controlling the temperature, solvent, and {[3,5-(CF3)2Pz]Cu}3 concentration, giving rise to luminescence thermochromism, luminescence solvatochromism, and a new optical phenomenon called “concentration luminochromism”, respectively.

Supramolecular Phosphorescent Trinuclear Copper(I) Pyrazolate Complexes for Vapochromic Chemosensors of Ethanol

“…4a). Such luminescent profile gave a large Stokes shift (∆λ) in 279, 304, 290, 322 and 338 nm, indicating the characteristics of phosphorescent compounds [21,[23][24][25][26][27][28][29][30][31][32][33][34]. Moreover, the luminescent decay measurements in excitation and emission maxima as shown in Fig.…”

“…5b were evaluated to give phosphorescent lifetime (τ) = 7.440.7, 7.601.5, 7.370.4, 8.690.3 and 8.161.8 μs at room temperature for complexes 2 A-E , respectively. Hence, complexes 2 A-E were successfully confirmed as phosphorescent compounds by metal-centered triplet excited states of the weak Cu(I)-Cu(I) metallophilic interaction [19,[23][24][25][26][27]. Considering the advantages of copper(I) complexes in their phosphorescence properties, it can be developed as promising vapochromic chemosensors based on changes in optical properties upon exposure to VOCs [35].…”

“…6f, green dot). Such quenching of intensity in 100% indicates that the chairlike coordination geometry of Cu(I)-Cu(I) metallophilic interaction [4,[19][20][21][22][23][24][25][26][27]35] was totally disrupted through the columnar assembly of the weak intermolecular interaction. In this case, Cu(I) ions in one pyrazole ring are unable to form metal-metal interaction with other Cu(I) ions of the ligand.…”

“…Therefore, these phenomena suggest that the molecular structure of chemosensors with a short alkyl side chain at the pyrazole ring of the complexes gave significant effect on the sensing capability with quenching phenomena toward the ethanol vapors. Since molecular size of ethanol is not large enough to cut-off the metal-metal interaction among pyrazolate molecules, such changes in emission spectra [3][4][5][12][13][14][15][16][17][18][19][20] and colors [4,12,35] in quenching phenomenon might be caused by the formation of a weak intermolecular hydrogen bonding interaction [4,13,[18][19][20][25][26][27]35] from OH of ethanol vapors with electronegative N and/or F atoms at the pyrazole ring so that the metal-metal interaction was totally disrupted and cannot form a bonding between the molecules. In the presence of bulky side chains from -CH 3 , the sensing capability will be reduced due to the influence of accessibility of ethanol vapors from that bulky group to be diffused to the emission center.…”

Modeling the Deposition of Metal Atoms on a p-Type Organometallic Conductor: Implications for Stability and Electron Transfer

“…Pt-T and Ru-T complexes are similar to Ni-T complexes where notable mixing of orbitals is seen and there is metal In conclusion, modeling the effect of electrode metal atom deposition onto a p-type gold trimer is important to understand the impact of metal-trimer chemistry upon the electronic properties of cyclo-Au(μ-L)] 3 . 7,11,12 Deposition of metal source and drain electrodes on the organometallic semiconductor during device fabrication is critical for stable device performance. Metal binding characteristics, as well as geometric and electronic properties, play an important role in minimizing impurity scattering within the device.…”