Bright Coppertunities: Multinuclear Cu<sup>I</sup> Complexes with N–P Ligands and Their Applications

Wallesch, Manuela; Volz, Daniel; Zink, Daniel M.; Schepers, Ute; Nieger, Martin; Baumann, Thomas; Bräse, Stefan

doi:10.1002/chem.201402060

Cited by 238 publications

(191 citation statements)

References 68 publications

(109 reference statements)

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“…The synthesis, structural and photophysical characterisations, as well as theoretical study of this copper iodide cluster formulated [Cu 6 I 6 (PPh 2 (CH 2 ) 3 PPh 2 ) 3 ] are presented. Comparative study with the clusters of derived geometries, namely, [Cu 4 I 4 (PPh 3 ) 4 ] cubane and open forms, was investigated to give insight into the luminescence properties (Chart 1). The structural differences of the clusters were analyzed by 63 Cu and 31 P solid-state nuclear magnetic resonance (NMR) spectroscopy.…”

Section: ■ Introductionmentioning

confidence: 99%

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

Benito¹,

Goff²,

Nocton³

et al. 2015

Inorg. Chem.

142

144

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An original copper(I) iodide cluster of novel geometry obtained by using a diphosphine ligand is reported and is formulated [Cu6I6(PPh2(CH2)3PPh2)3] (1). Interestingly, this sort of "eared cubane" cluster based on the [Cu6I6] inorganic core can be viewed as a combination of the two known [Cu4I4] units, namely, the cubane and the open-chair isomeric geometries. The synthesis, structural and photophysical characterisations, as well as theoretical study of this copper iodide along with the derived cubane (3) and open-chair (2) [Cu4I4(PPh3)4] forms, were investigated. A new polymorph of the cubane [Cu4I4(PPh3)4] cluster is indeed presented (3). The structural differences of the clusters were analyzed by solid-state nuclear magnetic resonance spectroscopy. Luminescence properties of the three clusters were studied in detail as a function of the temperature showing reversible luminescence thermochromism for 1 with an intense orange emission at room temperature. This behavior presents different feature compared to the cubane cluster and completely contrasts with the open isomer, which is almost nonemissive at room temperature. Indeed, the thermochromism of 1 differs by a concomitant increase of the two emission bands by lowering the temperature, in contrast to an equilibrium phenomenon for 3. The luminescence properties of 2 are very different by exhibiting only one single band when cooled. To rationalize the different optical properties observed, density functional theory calculations were performed for the three clusters giving straightforward explanation for the different luminescence thermochromism observed, which is attributed to different contributions of the ligands to the molecular orbitals. Comparison of 3 with its [Cu4I4(PPh3)4] cubane polymorphs highlights the sensibility of the emission properties to the cuprophilic interactions.

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Section: ■ Introductionmentioning

confidence: 99%

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

Benito¹,

Goff²,

Nocton³

et al. 2015

Inorg. Chem.

142

144

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“…[1][2][3][4][5] They are easily synthesized 6,7 and tunable in emission color, [8][9][10] with high emission quantum yields in the solid state. 7,10,11 Copper(I) halide compounds can be considered as a valid alternative to luminescent metal complexes of precious (i.e.…”

mentioning

confidence: 99%

Dual luminescence in solid CuI(piperazine): hypothesis of an emissive 1-D delocalized excited state

Maini

Braga

Mazzeo³

et al. 2015

Dalton Trans.

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Solid [CuI( piperazine) 0.5 ] ∞ , characterized by a structure with an infinite double chain of CuI, presents an unexpected dual luminescence. The short copper-copper distances allow the existence of both cluster-centered and 1-D delocalized electronic transitions, as emerged from theoretical calculations. Beyond the more common cluster-centered emission a higher energy band, which differs in lifetime and in temperature dependence, is observed.One of the most prominent classes of luminescent coordination compounds is that of copper(I) halides, due to their promising features for application in the field of optoelectronics. [1][2][3][4][5] They are easily synthesized 6,7 and tunable in emission color, [8][9][10] with high emission quantum yields in the solid state. 7,10,11 Copper(I) halide compounds can be considered as a valid alternative to luminescent metal complexes of precious (i.e. Ir or Os) and rare earth metals, which are expensive and environmentally problematic. 12 The luminescence properties of the copper halide clusters arise from a remarkable variety of emissive states, which have been extensively investigated in the last 30 years and can be summarized as follows: (a) a low-energy emission, attributed to a triplet cluster-centered ( 3 CC) excited state, is observed in the case of metal center interactions [13][14][15][16][17][18][19] and is independent of the nature of the ligand engaged in the complex; (b) a highenergy emission, attributed to a triplet halide-to-ligand charge transfer ( 3 XLCT) excited state, may show up in the presence of unsaturated ligands with accessible π-orbitals. 20 Moreover, recent studies have shown that several copper compounds present a thermally activated delayed fluorescence (TADF): Cu(I) halide-bridged compounds with P^N ligands are characterized by (metal + halide)-to-ligand charge transfer ((M + X) LCT) excited states where the low singlet-triplet energy gap allows emission from both the singlet and the triplet excited states, depending on the temperature. [21][22][23] The structure of [CuI( piperazine) 0.5 ] ∞ 24 is characterized by a one-dimensional copper iodide polymeric structure. The infinite double chain of CuI is described as castellated, 25 as shown in Fig. 1a, and the tetrahedral coordination of the copper(I) ions is fulfilled by the bridging piperazine to construct a 3D network (Fig. 1b and c). The inorganic chain is generated by the sequence of an inversion center and 2-fold axis symmetry elements, thus two different copper distances are present (2.771(1) Å and 2.729(1) Å). Although the presence of infinite double chain motifs has been observed in 20 struc-

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“…[21][22][23][24][25] Additionally, many Cu I complexes are known for their TADF properties, which can be exploited in the preparation of next-generation organic light-emitting diodes (OLEDs). [21,25,26] However, there are comparatively fewer examples containing Ag I and Au I as noted in a recent review by Tao et al [25] It is likely that the rarity of these TADF-exhibiting complexes, especially those of Au I , is due to the promotion of intersystem crossing to the excited triplet state through the heavy-atom effect. However, the photophysical process responsible for the aquamarine emission of the Au I -Cu I complex 3 at 343 K is unknown, and any assignment of TADF in 3 is purely speculative at this point.…”

Section: Discussionmentioning

confidence: 94%

Luminescent Thermochromism in a Gold(I)–Copper(I) Phosphine–Pyridine Complex

Chen

Catalano

2015

Eur J Inorg Chem

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The AuI complex [Au(Ph2PCH2py)2]BF4 (1) was prepared by mixing (tetrahydrothiophene)gold(I) chloride with 2‐[(diphenylphosphino)methyl]pyridine (Ph2PCH2py) in dichloromethane. The addition of [Cu(NCCH3)4]BF4 to 1 produced green‐luminescent [AuCu(Ph2PCH2py)2(NCCH3)2](BF4)2 (2). When crystals of 2 were exposed to air, two acetonitrile molecules were lost to form crystals of yellow‐luminescent [AuCu(Ph2PCH2py)2](BF4)2 (3). This simple solvent loss perturbs the environment around the CuI center, and the Au···Cu distance shortens from 3.3 to 2.8 Å. Crystallization of 2 or 3 from dichloromethane produced the two‐coordinate CuI–solvate complex, [AuCu(Ph2PCH2py)2](BF4)2·CH2Cl2 (3·CH2Cl2). Compound 3 exhibits temperature‐dependent emissions from 77 to 298 K (543 nm), 298 to 343 K (551 nm), and above 343 K (505 nm) that is reversed upon return to room temperature. The low‐temperature emission is typical of complexes with luminescent rigidochromic properties. However, based on differential scanning calorimetry, a phase change is responsible for the high‐temperature emission of 3.

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Bright Coppertunities: Multinuclear Cu^I Complexes with N–P Ligands and Their Applications

Cited by 238 publications

References 68 publications

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

Dual luminescence in solid CuI(piperazine): hypothesis of an emissive 1-D delocalized excited state

Luminescent Thermochromism in a Gold(I)–Copper(I) Phosphine–Pyridine Complex

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Bright Coppertunities: Multinuclear CuI Complexes with N–P Ligands and Their Applications

Cited by 238 publications

References 68 publications

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

Dual luminescence in solid CuI(piperazine): hypothesis of an emissive 1-D delocalized excited state

Luminescent Thermochromism in a Gold(I)–Copper(I) Phosphine–Pyridine Complex

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Bright Coppertunities: Multinuclear Cu^I Complexes with N–P Ligands and Their Applications