A chemopalette strategy for white light by modulating monomeric and excimeric phosphorescence of a simple Cu(<scp>i</scp>) cyclic trinuclear unit

Hu, Yang; Zheng, Ji; Peng, Su-Kao; Zhu, Xiaowei; Wan, Meng‐Yan; Lü, Weigang; Li, Dan

doi:10.1039/c9cc00716d

Cited by 26 publications

(48 citation statements)

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“…The radiative constant value is comparable to previously reported ones for copper(I) pyrazolates. 36…”

Section: Papermentioning

confidence: 99%

“…Copper(I) CTCs show phosphorescence due to emission from a metal-centered triplet state ( 3 MM) of an excimer, 31,32 and only very recently has it been reported that very high quantum yields, i.e., over 75%, are affordable in the crystal state at room temperature. [33][34][35][36] Although the planar structure of the metallacycle could facilitate the formation of columnar liquid crystal phases, liquid crystalline behaviour was not observed for copper(I) CTCs even on using the same ligands as those used for liquid crystalline silver(I) and gold(I) CTCs. 34 For example, silver(I) and gold(I) complexes with the 4-hexyl-3,5-dimethylpyrazolate ligand are liquid crystalline, but the copper(I) complex has a lower melting point and exhibits direct transition to the isotropic liquid.…”

Section: Introductionmentioning

confidence: 99%

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Liquid crystalline copper(i) complexes with bright room temperature phosphorescence

et al. 2020

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“…The radiative constant value is comparable to previously reported ones for copper(I) pyrazolates. 36…”

Section: Papermentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Liquid crystalline copper(i) complexes with bright room temperature phosphorescence

et al. 2020

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“…As far as trimers are concerned, the two main classes are isolated trimers and double trimers and we proposed to denote the latter as "3 + 3". The simplest derivatives of isolated trimers include CODBAB (4-Cl-pyrazolate) [40], VIJMUW (3,5-diMe-pyrazolate) [41], BELTOC (3,5-di-i-Pr-pyrazolate) [42] and XELXAN (3,5-di-CF3-pyrazolate) [43].…”

Section: Analysis Of the Reported Csd Structures (Hits) And Their Refmentioning

confidence: 99%

“…Simple examples of "3 + 3" double trimers ( Figure 4) are IDUYOW (3-Ph-pyrazolate) [44], TANRUW (3-CF3-pyrazolate) [32] and GITJIC (3,5-diMe-4-NO2-pyrazolate) [30] with near one bond between the triangles formed by Cu atoms and XOGJOU (4-NO2-pyrazolate) [45] with near three As far as trimers are concerned, the two main classes are isolated trimers and double trimers and we proposed to denote the latter as "3 + 3". The simplest derivatives of isolated trimers include CODBAB (4-Cl-pyrazolate) [40], VIJMUW (3,5-diMe-pyrazolate) [41], BELTOC (3,5-di-i-Pr-pyrazolate) [42] and XELXAN (3,5-di-CF 3 -pyrazolate) [43].…”

Section: Analysis Of the Reported Csd Structures (Hits) And Their Refmentioning

confidence: 99%

A Computational Study of Metallacycles Formed by Pyrazolate Ligands and the Coinage Metals M = Cu(I), Ag(I) and Au(I): (pzM)n for n = 2, 3, 4, 5 and 6. Comparison with Structures Reported in the Cambridge Crystallographic Data Center (CCDC)

Elguero

Alkorta

2020

Molecules

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The structures reported in the Cambridge Structural Database (CSD) for neutral metallacycles formed by coinage metals in their valence (I) (cations) and pyrazolate anions were examined. Depending on the metal, dimers and trimers are the most common but some larger rings have also been reported, although some of the larger structures are not devoid of ambiguity. M06-2x calculations were carried out on simplified structures (without C-substituents on the pyrazolate rings) in order to facilitate a comparison with the reported X-ray structures (geometries and energies). The problems of stability of the different ring sizes were also analyzed.

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“…In fact, the observation of luminescence is quite typical for multinuclear coinage metal d 10 complexes with M3 units. [394][395][396][397][398][399][400][401][402][403][404][405][406][407][408][409] Figure 6.17: Luminescence properties of 9 H in MeCN at room temperature under inert conditions. Left: Emission spectra of 9 H (0.125 mM, solid green) and [Cp2Co](PF6) (0.884 mM, solid black) upon excitation at 342 nm normalized to Imax, as well as ∆(I/Imax) of 9 H (dotted green) with respect to the spectrum of [Cp2Co](PF6).…”

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confidence: 99%

Transformations of Energy-Related Small Molecules at Dinuclear Complexes

Lücken¹

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The urgent need for the development of carbon-neutral energy conversion schemes has inspired chemists worldwide to investigate catalytic water splitting using sunlight as the energy source. A key component for the preparation of devices employing this process is the water oxidation catalyst (WOC), and understanding the factors that govern its catalytic performance is among the major challenges. Beyond the well-established WOCs based on ruthenium, catalysts containing abundant first-row transition metals are a desirable target but require a deeper understanding before their large-scale application is viable. Along these lines, this work focusses on both the in-depth analysis of diruthenium WOCs, as well as the search for new catalysts based on copper and cobalt. A glance is also cast at dioxygen activation by dicopper complexes, which is not only of interest on its own but can additionally provide insight into intermediates that are relevant to water oxidation. emphasizes the necessity for oxidatively robust ligand systems. In addition to the analysis of the electrocatalytic water oxidation ability, magnetic susceptibility measurements were conducted for several of the dicopper and dicobalt complexes bearing the pyrazolate/tacn hybrid ligands, viz. 7 MeCN , 5 HCO2 and its acetate-bridged congener 5 OAc as well as the (L 2b ) − -ligated dicobalt analogs 8 HCO2 and 8 OAc . Interestingly, 8 HCO2 and 8 OAc feature slow relaxation of magnetization with relaxation times τ0 of 7.7•10 −6 s −1 and 3.7•10 −6 s −1 , as well as energy barriers Ueff of 8.9 and 6.0 cm −1 , respectively, and thus belong to a very small circle of homodinuclear cobalt(II) complexes with SMM behavior.5 OAc and 5 HCO2 were further investigated in regard to dioxygen activation following the strategy: (i) reduction of the dicopper(II) complex for the in situ generation of a dicopper(I) species (5 I/I ) and (ii) addition of dry O2 to 5 I/I for copper-oxygen adduct formation. Surprisingly, reduction of 5 OAc to 5 I/I affords a mixed-valent Cu I Cu II intermediate (5 I/II ), characterized both by UV/vis and EPR spectroscopy. This observation is unprecedented for dinuclear copper complexes bearing pyrazolate/tacn hybrid ligands and is attributed to the acetate unit in the bimetallic pocket, which is proposed to change its coordination mode from bridging to chelating upon one-electron reduction in order to stabilize the Cu II site. Addition of molecular oxygen to 5 I/II monitored by time-resolved UV/vis spectroscopy in a stopped-flow setup at −40 °C results in a superoxo species (5 S ) as primary Cu II 2O2 adduct, in line with a 1e − reduction of the dioxygen. The generated 5 S rapidly converts to a µ-1,2-peroxo compound (5 P ), distinguished by its characteristic UV/vis-spectroscopic features, by reduction with either an additional 5 I/II species or a second 5 S compound. On the other hand, 5 P is directly formed when exposing 5 I/I to O2, and can be electrochemically oxidized at −0.55 V vs. Fc +/0 (O2 2− /O2 •− redox couple) at −45 °C in MeCN. The low st...

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A chemopalette strategy for white light by modulating monomeric and excimeric phosphorescence of a simple Cu(i) cyclic trinuclear unit

Abstract: Cu3(4-chloropyrazolate)3 is presented herein to exhibit unprecedented room-temperature white phosphorescence by modulating monomeric blue and excimeric yellow phosphorescence.

Cited by 26 publications

References 27 publications

Liquid crystalline copper(i) complexes with bright room temperature phosphorescence

Liquid crystalline copper(i) complexes with bright room temperature phosphorescence

A Computational Study of Metallacycles Formed by Pyrazolate Ligands and the Coinage Metals M = Cu(I), Ag(I) and Au(I): (pzM)n for n = 2, 3, 4, 5 and 6. Comparison with Structures Reported in the Cambridge Crystallographic Data Center (CCDC)

Transformations of Energy-Related Small Molecules at Dinuclear Complexes

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