Reversible stimuli-responsive chromism of a cyclometallated platinum(<scp>ii</scp>) complex

Zheng, Qingshu; Borsley, Stefan; Tu, Tao; Cockroft, Scott L.

doi:10.1039/d0cc06775j

Cited by 16 publications

(9 citation statements)

References 50 publications

(63 reference statements)

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“…Square planar d 8 platinum complexes have recently drawn considerable interest because of their intriguing light-emitting and assembly properties. − Platinum complexes often display phosphorescent emissions due to the strong spin–orbit coupling of the platinum atom. By tuning the ligand structure and coordination mode, full-color emissive platinum complexes have been synthesized and investigated. − The assembly properties of platinum complexes are mostly associated with their tendency to form π–π and Pt–Pt interactions upon aggregation. − In this context, a great number of platinum complexes have been reported to display appealing assembly behavior with tunable emission properties. − …”

Section: Introductionmentioning

confidence: 99%

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A Carbazole-Bridged Biscyclometalated Diplatinum Complex: Synthesis, Characterization, and Dual-Mode Aggregation-Enhanced Phosphorescence

2021

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A cationic carbazole-bridged biscyclometalated diplatinum complex 4 has been synthesized and characterized. Single-crystal X-ray analysis demonstrates that complex 4 displays a dimeric structure with noncovalent π–π stacking and unique double Pt–Pt interactions. In aerated dilute CH3CN, complex 4 is characterized by a very weak monomeric yellow emission (λemi = 547 nm; Φ = 0.51%), which is attributed to the triplet intraligand (3LC) excited state mixing with some charge transfer characters. In contrast, under aerated conditions, the dispersion of 4 in a mixed solvent of CH3CN/Et2O (1/9, v/v) or CH3CN/H2O (1/9, v/v) displays intense yellow (λemi = 550 nm; Φ = 35.5%; τ = 11.10 μs) and red emission (λemi = 635 nm; Φ = 14.1%; τ = 7.00 μs), respectively. These aggregation-induced phosphorescent emission enhancements are considered being caused by the oxygen-shielding effect and the molecular rigidification-induced decrease of nonradiative decays in the aggregate state. The morphology and size of the aggregates under these two conditions are examined by scanning electron microscope and dynamic light scattering analysis. The absorption and emission properties of 4 are further rationalized by time-dependent density functional theory calculations on a model compound.

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Section: Introductionmentioning

confidence: 99%

“…13 C NMR (100 MHz, CDCl 3 ): δ 14.13, 22.68, 26.10, 27.82, 28.63, 28.74, 29.27, 29.34, 29.39, 29.53, 29.61, 29.72, 31.90, 46.76, 119.00, 120.30, 121.46, 122.13, 125.04, 126.11, 126.35, 128.23, 131.14, 136.27, 136.74, 140.05, 149.06, 149.59, 157.62, 159.17. ESI-HRMS calcd for C 44 H 45 N 5 •Na: 666.3573.…”

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confidence: 99%

A Carbazole-Bridged Biscyclometalated Diplatinum Complex: Synthesis, Characterization, and Dual-Mode Aggregation-Enhanced Phosphorescence

2021

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“…In fact, the collected solid‐state structures revealed the impact of solvent molecules on the inter‐platinum distance and color of the system (Figure 10c). Solvent polarity has also been employed to cause reversible dimerization of cyclometalated Pt(II) complexes to elicit chromism in solution [89] …”

Section: Solventmentioning

confidence: 99%

Chromic Platinum Complexes Containing Multidentate Ligands

2021

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Platinum(II) complexes display versatile chromic behavior as a consequence of their square planar geometry, which enables intra‐ and intermolecular Pt⋅⋅⋅Pt interactions via open axial coordination sites. These metallophilic interactions are known to generate metal‐metal‐to‐ligand‐charge transfer (MMLCT) transitions, in addition to the ligand‐to‐ligand charge transfer (LLCT) and metal‐to‐ligand‐charge‐transfer (MLCT) transitions that are already present. The electronic properties of such complexes, and consequently the magnitude and intensity of these transitions, can be modulated by various functional groups as well as environmental factors, affording control over the color and luminescence. The responsive behavior of these complexes makes them attractive candidates for chromic devices with applications in memory, encryption, sensors, and optoelectronics. This Minireview summarizes the mechanisms and reversibility of optical chromism in platinum(II) complexes, with a focus on the recent developments in the literature.

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“…Luminescent cyclometalated Pt(II) complexes with square planar geometry have received great research attention for their unique photophysical properties with applications in various fields, including light‐emitting diodes, sensors, and photocatalysis. [ 2 ] For instance, a variety of responsive systems to one or multiple stimuli based on cyclometalated Pt(II) complexes have been developed for sensing applications, [ 3 ] including thermochromic, [ 4 ] solvatochromic, [ 5 ] mechanochromic,[4a] and vapochromic complexes. [ 6 ] The square planar geometry of these complexes could enable their self‐assembly through metal–metal (Pt⋯Pt) interactions, which subsequently affect their photophysical properties [2b].…”

Section: Introductionmentioning

confidence: 99%

Color Tuning of Luminescent Cationic Platinum(II) Complexes: Effects of Molecular Structures and Counter‐Anions

et al. 2022

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The photophysical properties of square planar Pt(II) complexes are often strongly dependent on their self‐assembly modes and intermolecular Pt⋯Pt interactions. Controlling these interactions is important to achieve valuable properties for various applications, such as light‐emitting diodes and environmental sensing devices. Herein, a series of highly luminescent ionic Pt(II) complexes with tunable emission colors are reported, by controlling the molecular structures and interactions in solid state. Four ionic Pt(II) complexes, with a general formula [Pt(C^N)(N^N)]+X− (C^N = 2‐phenylpyridine or 2‐(2,4‐difluorophenyl)pyridine; N^N = 2,2′‐bipyridine; X−= chloride (Cl−) or tetraphenylborate (BPh4−), are designed, synthesized, and characterized. Due to the presence of intermolecular Pt⋯Pt interactions, strong metal–metal‐to‐ligand charge transfer (MMLCT) emissions are recorded in all four complexes with color changing from green to deep red in solid state. A high photoluminescence quantum efficiency (PLQE) of 81% is achieved for one of the complexes containing large BPh4− anions, due to the site isolation effects. Detailed structural and photophysical characterizations reveal a clear correlation between the stacking of these Pt(II) complexes and their photophysical properties, which can be well regulated by the molecular structures and counter‐anions.

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Reversible stimuli-responsive chromism of a cyclometallated platinum(ii) complex

Abstract: We report the reversible chromism and luminesence of a cyclometalated platinum(II) complex that forms dimers, with close Pt···Pt interactions that can be modulated in response to solvent and temperature. The...

Cited by 16 publications

References 50 publications

A Carbazole-Bridged Biscyclometalated Diplatinum Complex: Synthesis, Characterization, and Dual-Mode Aggregation-Enhanced Phosphorescence

A Carbazole-Bridged Biscyclometalated Diplatinum Complex: Synthesis, Characterization, and Dual-Mode Aggregation-Enhanced Phosphorescence

Chromic Platinum Complexes Containing Multidentate Ligands

Color Tuning of Luminescent Cationic Platinum(II) Complexes: Effects of Molecular Structures and Counter‐Anions

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