Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu4I6} clusters from [alkyl-P(2-Py)3]+ salts and CuI: when size matters

Artem’ev, Alexander V.; Pritchina, Elena A.; Рахманова, М. И.; Gritsan, Nina P.; Bagryanskaya, I. Yu.; Малышева, С. Ф.; Белогорлова, Н. А.

doi:10.1039/c8dt04328k

Cited by 46 publications

(54 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…33 Another binuclear anion is [Cu2I4] 2which has been encountered in several associations with different organic and inorganic cations. 34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66 The photophysical properties of these compounds have been rarely characterized, [Cu2I4] 2being simply treated as an inorganic counter-anion and not as an emissive species by itself. In particular, with the tetraphenylphosphonium cation, the polymorphic structure of (PPh4)2[Cu2I4] has been reported but no photophysical characterization has been investigated.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2020

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

“…63 Cu static WURST-QCPMG NMR spectra of (PPh4)2[Cu2I4]-A, B and Bg. The span of the patterns is about 9000 ppm, corresponding to ca 1.7 MHz.…”

mentioning

confidence: 99%

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

et al. 2020

View full text Add to dashboard Cite

show abstract

“…The results are consistent with those found for 1D-AIO structures. 35 Although the ESI-MS(−) spectra of both pure ionic hybrid structures and AIO structures share similar features, namely the characteristic peaks for [Cu n I n +1 ] − anions ( n = 2 to 12), the ESI-MS(+) spectra clearly distinguish AIO compounds from ionic structures. Only the spectra of AIO structures exhibit dominating signals assigned to the [(L) 3 Cu m I m +2 ] + cations ( n = 4–9).…”

Section: Important Properties Of Aio Compoundsmentioning

confidence: 98%

“…The size of alkyl substituent in the ligands appears to be important in the formation of AIO-type compounds. 35 For example, Pr-tpp , Bu-tpp and Bn-tpp (Bn = benzyl group) lead to AIO-type structures, while Me-tpp directs to an ionic complex.…”

Section: Crystal Structures Of Aio-type Compoundsmentioning

confidence: 99%

See 1 more Smart Citation

All-in-one: a new approach toward robust and solution-processable copper halide hybrid semiconductors by integrating covalent, coordinate and ionic bonds in their structures

Hei

2021

Chem. Sci.

View full text Add to dashboard Cite

show abstract

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

View full text Add to dashboard Cite

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.

show abstract

Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu₄I₆} clusters from [alkyl-P(2-Py)₃]⁺ salts and CuI: when size matters

Abstract: First examples of zwitterionic CuI-based complexes showing red photoluminescence are reported.

Cited by 46 publications

References 45 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]

All-in-one: a new approach toward robust and solution-processable copper halide hybrid semiconductors by integrating covalent, coordinate and ionic bonds in their structures

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

Contact Info

Product

Resources

About

Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu4I6} clusters from [alkyl-P(2-Py)3]+ salts and CuI: when size matters

Abstract: First examples of zwitterionic CuI-based complexes showing red photoluminescence are reported.

Cited by 46 publications

References 45 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]

All-in-one: a new approach toward robust and solution-processable copper halide hybrid semiconductors by integrating covalent, coordinate and ionic bonds in their structures

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

Contact Info

Product

Resources

About

Alkyl-dependent self-assembly of the first red-emitting zwitterionic {Cu₄I₆} clusters from [alkyl-P(2-Py)₃]⁺ salts and CuI: when size matters

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