Luminescent Cyclometalated Platinum Complexes with π-Bonded Catecholate Organometallic Ligands

Moussa, Jamal; Loch, Aruny; Chamoreau, Lise‐Marie; Esposti, Alessandra Degli; Bandini, Elisa; Barbieri, Andrea; Amouri, Hani

doi:10.1021/acs.inorgchem.6b02731

Cited by 21 publications

(9 citation statements)

References 71 publications

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“…From this point of view a topology of ligand that provides an opportunity for synthesis of coordination polymers or an ordering of the molecules in the crystal phase may be very useful. o-Quinone itself might be a bridging ligand in case of binding of metal ions both by dioxolene site and by π-complexation with diene system [5][6][7][8][9][10]. The chemistry of o-quinones is immensely rich and diverse, so there are many ways to functionalize an o-quinone molecule.…”

Section: Of 28mentioning

confidence: 99%

Functionalized o-Quinones: Concepts, Achievements and Prospects

Martyanov¹,

Kuropatov²

2018

Inorganics

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o-Quinones are both well-studied and promising redox-active chelating ligands. There are plenty of interesting effects to be found on o-quinone-derived metallocomplexes, such as photo-thermo mechanical effect in solid phase and in solution, luminescence, SMM properties and so on. A combination o-quinone function with an additional coordination site or redox active fragment in the same molecule might sufficiently extend an assembling as well as functional capability of such ligand in complexes. In this paper, the authors focus on o-quinones decorated with additional non-dioxolene chelating coordination site or with electron donor redox active annelated fragments.

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Section: Of 28mentioning

confidence: 99%

Functionalized o-Quinones: Concepts, Achievements and Prospects

Martyanov¹,

Kuropatov²

2018

Inorganics

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“…The use of organometallic ligands for the design of new materials often leads to the formation of heteropolymetallic species benefiting from the specific properties of the various metallic centers . This field is dominated by ferrocenyl-, − (η 5 -cyclopentadienyl)metal-, and (η 6 -benzene)metal-containing pendant or linkage groups. − The commonly reported properties are, for instance, luminescence (also including near-IR emission), magneticity, catalysis, and recently theranostics. , Coordination polymers, , metal organometallic frameworks (MOMFs), , and nanocomposites, which are the entries to functional materials, have also been prepared using these types of ligands. Concurrently, the synthesis and investigations of other types of organometallic ligands were reported, and multiple functional materials, including MOMFs, − have been designed.…”

Section: Introductionmentioning

confidence: 99%

A Platinum(II) Organometallic Building Block for the Design of Emissive Copper(I) and Silver(I) Coordination Polymers

2020

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The tritopic organometallic ligand trans-MeSC6H4CCPt(PMe3)2(CN) (L1) was prepared from cis-PtCl2(PMe3)2 and p-ethynyl(methyl thioether)benzene. Its versatility was shown with the formation of [CuX(L1)] n coordination polymers (CPs) with CuX salts in MeCN (X = I (CP1), CN (CP2), SCN (CP3)). These CPs were characterized by X-ray crystallography, thermal gravimetric analysis (TGA), and IR and Raman spectroscopy. CP1 consists of a 1D head-to-tail chain formed by tricoordinated −CN–CuI(η2-CC)– linkages, whereas CP2 is built upon a central (CuCN) n zigzag chain bearing dangling L1s held by −CN–Cu bonds. Finally, CP3 exhibits 2D sheets secured by Cu–NC–/–(Me)S–Cu bondings and transversal Cu–S–CN–Cu bridges. Concurrently, the CPs formed with AgX (X = NO3 – (CP4 and CP5), CF3CO2 – (CP6) PF6 – (CP7)) exhibits 2D sheets with guest molecules (anion, solvents) inside the tight pores or between layers. These new materials are emissive: L1 (λ0–0 ∼465 nm), CP1–CP7 (500 < λmax < 620 nm). Their photophysical properties (absorption and emission spectra, emission lifetimes (∼0.2 < τe < 120 μs), and quantum yields in the solid state at 77 and 298 K) were analyzed. The various natures of the emissive excited states were addressed by density functional theory (DFT) and time-dependent DFT (TDDFT) computations. For CP1, this state is a triplet halide or pseudohalide to ligand charge transfer 3XLCT (CT = charge transfer; X = I; L = L1) and for CP2, it is 3XLCT (X = CN; L = L1). However, for CP3, it is 3XLCT (X = SCN; L = L1). For CP4, the T1 state is described as a [MeSC6H4(η2-CC)-Ag(NO3)]2 → [Pt]/CCC6H4SMe CT.

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“…The luminescence properties of the cyclometalated platinum(II) complexes make them appropriate candidates for investigation by many research groups . Regarding these properties, cycloplatinated(II) complexes have various applications such as in light‐emitting devices, dye‐sensitized solar cells, photoswitches, photocatalysts and chemical or biochemical sensors .…”

Section: Introductionmentioning

confidence: 99%

Strong red emissions induced by Pt–Pt interactions in binuclear cycloplatinated(II) complexes containing bridging diphosphines

Nazari

Shahsavari

2019

Applied Organom Chemis

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A series of dinuclear cycloplatinated(II) complexes with general closed formula of [Pt 2 Me 2 (C^N) 2 (μ-P^P)] (C^N = 2-vinylpyridine (Vpy), 2,2′bipyridine N-oxide (O-bpy), 2-(2,4-difluorophenyl)pyridine (dfppy); P^P = 1,1bis(diphenylphosphino)methane (dppm), N,N-bis(diphenylphosphino)amine (dppa)) are reported. The complexes were characterized by means of NMR spectroscopy. Due to the presence of dppm and dppa with short backbones as bridging ligands, two platinum centres are located in front of each other in these complexes so a Pt…Pt interaction is established. Because of this Pt…Pt interaction, the complexes have bright orange colour under ambient light and are able to strongly emit red light under UV light exposure. These strong red emissions originate from a 3 MMLCT (metal-metal-to-ligand charge transfer) electronic transition. In most of these complexes, the emissions have unstructured bell-shaped bands, confirming the presence of large amount of 3 MMLCT character in the emissive state. Only the complexes bearing dfppy and dppa ligands reveal dual luminescence: a high-energy structured emission originating from 3 ILCT/ 3 MLCT (intra-ligand charge transfer/metal-to-ligand charge transfer) and an unstructured low-energy band associated with 3 MMLCT. In order to describe the nature of the electronic transitions, density functional theory calculations were performed for all the complexes. /journal/aoc 1 of 11 3 J PtH = 41.6 Hz, 2 J PH = 10.6 Hz, 2H, CH 2 of dppm), 6.28 (t, 3 J HH = 6.7 Hz, 2H, H 5 ), 6.38 (m, 3 J FH = 10.6 Hz, 4 J HH = 1.5 Hz, 2H, H 3' ), 6.67 (m, 3 J PtH = 62.4 Hz, 2H, H 5' ), 7. 28-7.34 (m, 12 H, H m and H p of dppm), 7.43 (t, 3 J HH = 7.9 Hz, 2H, H 4 ), 7.68 (d, 3 J PtH = 19.3 Hz, 3 J HH = 5.8 Hz, 2H, H 6 ), 7.73 (d, 3 J HH = 7.9 Hz, 2H, H 3 ), 7.78-7.81 (m, 8H, H o of dppm); δ ( 19 F{ 1 H}) −110.1 (m, 4 J PtF = 78 Hz, 2F, F 2' ), −110.5 (m, 4 J PtF = 51 Hz, 2F, F 4' ); δ ( 31 P{ 1 H}) 22.9 (m, 1 J PtP = 2202 Hz, 3 J PtP = 34 Hz, 2 J PP = 54 Hz, 2P, dppm).

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Luminescent Cyclometalated Platinum Complexes with π-Bonded Catecholate Organometallic Ligands

Cited by 21 publications

References 71 publications

Functionalized o-Quinones: Concepts, Achievements and Prospects

Functionalized o-Quinones: Concepts, Achievements and Prospects

A Platinum(II) Organometallic Building Block for the Design of Emissive Copper(I) and Silver(I) Coordination Polymers

Strong red emissions induced by Pt–Pt interactions in binuclear cycloplatinated(II) complexes containing bridging diphosphines

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