Luminescence Vapochromism of a Dynamic Copper Iodide Mesocate

Benito, Quentin; Balogh, Cristina M.; Moll, Hani El; Gacoin, Thierry; Cordier, Marie; Rakhmatullin, Aydar; Latouche, Camille; Martineau‐Corcos, Charlotte; Perruchas, Sandrine

doi:10.1002/chem.201804377

Cited by 16 publications

(11 citation statements)

References 39 publications

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“…Actually, their potential applications as sensors, − photocatalytic systems, and emitters in organic light-emitting diodes (OLEDs) − have been recently reported. Copper(I) iodide compounds can also display diverse stimuli-responsive properties such as luminescence thermochromism, , mechanochromism, , rigidochromism, or vapo-/solvatochromism . Combining multistimuli-responsive properties is actually particularly appealing to access original multifunctional materials.…”

Section: Introductionmentioning

confidence: 99%

Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh₄)₂[Cu₂I₄]

et al. 2020

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The photoluminescent stimuli-responsive properties of two crystalline polymorphs of (PPh4)2[Cu2I4] formula, are reported. Distinct luminescence properties are exhibited by these ionic copper iodide compounds with blue or yellow emission and original luminescence thermochromism and mechanochromism are demonstrated. While one polymorph displays contrasted temperature-dependent emission properties, the other shows great modification of its emission upon mechanical solicitation. Establishment of structure-properties relationships supported by theoretical approach, permit to get insights into the origin of the photoluminescence properties and the mechanisms at play. According to DFT calculations, the different emission bands originate either from the (PPh4) + organic cation or from the [Cu2I4] 2anion. Activation of these two emissive centers appears to be dependent on the crystalline packing of the polymorph. The thermochromism displayed by one polymorph can be attributed to variation in temperature of the relative intensities of two emission bands of two different excited states. The origin is different for the other polymorph with emission bands coming from two independent emissive centers namely, (PPh4) + and [Cu2I4] 2-. The luminescence mechanochromism is attributed to a polymorphic transition. The mechanical solicitation induces a partial transformation of one polymorph into the other within a disordered phase. The mechanochromic mechanism can be related to mechanical modifications of inter-molecular interactions between the (PPh4) + cations. By displaying luminescence properties that dependent on crystalline structure, excitation wavelength, temperature and mechanical solicitation, the studied copper iodides offer a great possibility of emissive color control and switch, a clear demonstration of great potentialities of this family of compounds for developing photoactive materials.

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Section: Introductionmentioning

confidence: 99%

Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh₄)₂[Cu₂I₄]

et al. 2020

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“…This method has demonstrated coherent results with respect to experimental data. 76,[88][89][90] In the present case, the relaxed excited state geometry still presents relatively long Cu-Cu distances (mean value of 3.343 Å). The Cu-I and Cu-P distances are also barely modified from the ground state to the excited one (Table S6).…”

Section: Resultsmentioning

confidence: 47%

Mechanically responsive luminescent films based on copper iodide clusters

et al. 2021

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“…This can allow thermal population of the lowest energy excited singlet state (S 1 ) from the lowest energy triplet excited state (T 1 ), via a reverse intersystem crossing (RISC) inducing efficient radiative relaxation to the ground state and exalted solid‐state luminescence properties that occurs ideally at temperatures close to room temperature (RT). Importantly, this phenomenon is not only observed for mononuclear Cu(I) complexes but several polynuclear Cu I complexes have been also reported with enhanced solid‐state luminescent properties [5b,9n–x, 10d–j] . In such derivatives non‐covalent short intermetallic cuprophilic interactions (d(Cu−Cu) bellow ca.…”

Section: Introductionmentioning

confidence: 92%

Impact of Intermolecular Non‐Covalent Interactions in a Cu^I₈Pd^II₁ Discrete Assembly: Conformers’ Geometries and Stimuli‐Sensitive Luminescence Properties

Moutier

Schiller

Lecourt

et al. 2022

Chemistry A European J

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A new highly solid-state luminescent phase of a previously reported weakly luminescent Cu I 8 Pd II 1 dicationic assembly is reported revealing the high geometrical versatility of this moiety that importantly alters its luminescent properties. This very minor new species B c is based on a different conformer scaffold than the one encountered in the previously reported B o form and, essentially differs from B o by displaying shorter Cu I -Cu I intermetallic distances. DFT calculations allow concluding that the predominance in the solidstate of the weakly luminescent and less stable B o phase is due to the extra stability induced by a larger number of intermolecular non-covalent π-CH interactions in its crystalline packing and not by the intrinsic stability of the Cu I 8 Pd II 1 dicationic moiety. Calculations also revealed that a more stable conformation B calc is expected in vacuum, which bears a different distribution of Cu I -Cu I intermetallic distances than the dications in B o and B c phases. Taking into account that the geometrical alterations are associated to drastic changes of luminescence properties, this confer to the Cu I 8 Pd II 1 assembly high potentiality as stimuli-sensitive luminescent materials. Indeed, by applying mechanical or thermal stress to samples of B o phase, new phases B g and B m , respectively, were obtained. Alterations of the solid-state photophysical properties of these new species compared to those recorded for B o are reported together with a combined experimental and computed study of the structures/properties relationships observed in these phases.

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Luminescence Vapochromism of a Dynamic Copper Iodide Mesocate

Cited by 16 publications

References 39 publications

Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh₄)₂[Cu₂I₄]

Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh₄)₂[Cu₂I₄]

Mechanically responsive luminescent films based on copper iodide clusters

Impact of Intermolecular Non‐Covalent Interactions in a Cu^I₈Pd^II₁ Discrete Assembly: Conformers’ Geometries and Stimuli‐Sensitive Luminescence Properties

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Luminescence Vapochromism of a Dynamic Copper Iodide Mesocate

Cited by 16 publications

References 39 publications

Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh4)2[Cu2I4]

Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh4)2[Cu2I4]

Mechanically responsive luminescent films based on copper iodide clusters

Impact of Intermolecular Non‐Covalent Interactions in a CuI8PdII1 Discrete Assembly: Conformers’ Geometries and Stimuli‐Sensitive Luminescence Properties

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Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh₄)₂[Cu₂I₄]

Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh₄)₂[Cu₂I₄]

Impact of Intermolecular Non‐Covalent Interactions in a Cu^I₈Pd^II₁ Discrete Assembly: Conformers’ Geometries and Stimuli‐Sensitive Luminescence Properties