trans Bis-N-heterocyclic carbene bis-acetylide palladium(II) complexes

Koch, Michael; Garg, Jai Anand; Blacque, Olivier; Venkatesan, Koushik

doi:10.1016/j.jorganchem.2011.12.002

Cited by 8 publications

(12 citation statements)

References 53 publications

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“…The trans ‐angles are linear, 180.00(18)° in C−Pd‐C and 180° in Br−Pd−Br. The Pd−C (2.025(6) and 2.026(6) Å) and Pd−Br (2.4358(8) Å) bond distances are comparable to those found in other trans bi‐carbene complexes [8a,,11c] . The N−C(O) bond distance is 1.315(10) Å, shorter than the sum of the individual single bond covalent radii of C (0.772 Å) and N (0.70 Å), [16] reflecting the partial double bond character of the amido substituent.…”

Section: Resultssupporting

confidence: 58%

Synthesis and Structures of Benzyl‐ and Amido‐Substituted N‐Heterocyclic Palladium Carbene Complexes

Wang

Yang²,

Chang

et al. 2022

ChemistrySelect

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The benzyl-and amido-substituted benzimidazolium ligand precursor [Bz-BimH-CH 2 CONH 2 ]Br (1) was synthesized. Under different conditions, the reactions of this ligand precursor with PdBr 2 produced palladium carbene complexes: Pd 5). These complexes were characterized by NMR, IR, and singlecrystal X-ray diffraction analyses. Complex 2 contains two trans rotamers in both the solution and solid state, and a crystal that possesses a trans-anti conformation is confirmed through single-crystal X-ray diffraction analysis. Complex 3 contains two cis-orientated bidentate carbene ligands, and complexes 4 and 5 are mono-carbene complexes. The chelate rings in complex 3 rendered the methylene protons of the amido-substituted diastereotopic, and a long range (six bond) through bond interaction between the carbonyl carbon and the methylene protons of the benzyl-substituent was observed through the HMBC experiment. The catalytic activity studies indicated 4 and 5 are better catalysts in Suzuki-Miyaura coupling reaction.

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Section: Resultssupporting

confidence: 58%

Synthesis and Structures of Benzyl‐ and Amido‐Substituted N‐Heterocyclic Palladium Carbene Complexes

Wang

Yang²,

Chang

et al. 2022

ChemistrySelect

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“…20). 62,63 The UV-Vis spectra of the palladium complexes 47 revealed great spectral changes depending on the nature of the acetylide ligands. The platinum complexes 48 were emissive at room temperature and the TD-DFT studies confirmed tunable lowest lying emissive states, assigned to predominantly metal-perturbed ligand-to-ligand 3 LLCT (p alkp alk ) character and to a lesser extent 3 MLCT (dp alk ).…”

Section: +mentioning

confidence: 99%

N-heterocyclic carbene metal complexes: photoluminescence and applications

2014

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This review covers the advances made in the synthesis of luminescent transition metal complexes containing N-heterocyclic carbene (NHC) ligands. The presence of a high field strength ligand such as an NHC in the complexes gives rise to high energy emissions, and consequently, to the desired blue colour needed for OLED applications. Furthermore, the great versatility of NHC ligands for structural modifications, together with the use of other ancillary ligands in the complex, provides numerous possibilities for the synthesis of phosphorescent materials, with emission colours over the entire visible spectra and potential future applications in fields such as photochemical water-splitting, chemosensors, dye-sensitised solar cells, oxygen sensors, and medicine.

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“…Exquisite control of the steric environment and electronic properties can be achieved by rational modification of the substituents on the nitrogen atoms and the NHC framework 25. Following the report of Strassner and co‐workers on dicationic blue‐light‐emitting tetra‐NHC Pt II complexes,1d, 26 we recently described the preparation and photophysical investigation of a series of neutral bis‐NHC Pt II acetylide and bis‐NHC Pd II acetylide complexes 27. Some of the bis‐NHC Pt II ‐acetylides displayed blue emission at room temperature and the luminescent properties were found to be tunable by changing the functional group on the alkyne 28.…”

Section: Introductionmentioning

confidence: 99%

“…[25] Following the report of Strassner and co-workers on dicationic blue-light-emitting tetra-NHC Pt II complexes, [1d, 26] we recently described the preparation and photophysical investigation of a series of neutral bis-NHC Pt II acetylide and bis-NHC Pd II acetylide complexes. [27] Some of the bis-NHC Pt IIacetylides displayed blue emission at room temperature and the luminescent properties were found to be tunable by changing the functional group on the alkyne. [28] TD-DFT calculations revealed that the emission was dominated by intraA C H T U N G T R E N N U N G liA C H T U N G T R E N N U N G gand charge transfer 3 A C H T U N G T R E N N U N G [p!p*A C H T U N G T R E N N U N G (C CR)] ( 3 IL), with limited participation of the metal center in the excited state.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene Pt^II Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies

Zhang

Blacque

Venkatesan

2013

Chemistry A European J

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We have synthesized cis and trans N-heterocyclic carbene (NHC) platinum(II) complexes bearing σ-alkynyl ancillary ligands, namely [Pt(dbim)2 (CCR)2 ] [DBIM=N,N'-didodecylbenzimidazoline-2-ylidene; R=C6 H4 F (4), C6 H5 (5), C6 H2 (OMe)3 (6), C4 H3 S (7), and C6 H4 CCC6 H5 (8)] and [Pt(ibim)2 (CCC6 H5 )2 ] (9) (ibim=N,N'-diisopropylbenzimidazoline-2-ylidene), starting from [Pt(cod)(CCR)2 ] (COD=cyclooctadiene) and 2 equivalents of [dbimH]Br ([ibimH]Br for complexes 9) in the presence of tBuOK and THF. Mechanistic investigations aimed at uncovering the cis to trans isomerization reaction have been performed on the representative cis complex 5 a [Pt(dbim)2 (CCC6 H5 )2 ] and revealed the isomerization to progress smoothly in good yield when 5 a was treated with catalytic amounts of [Pt(cod)(CCR)2 ] at 75 °C in THF or when 5 a was heated at 200 °C in the solid state under an inert atmosphere. Detailed examination of the reactions points to the possible involvement, in a catalytic fashion, of a solvent-stabilized Pt(II) dialkyne complex in the former case and a Pt(0) NHC complex in the latter case, for the transformation of the cis isomer to the corresponding trans complex. Thermal stability and the isomerization process in the solid state have been further investigated on the basis of TGA and DSC measurements. X-ray diffraction studies have been carried out to confirm the solid-state structures of 4 b, 5 a, 5 b, and 9 b. All of the synthesized dialkyne complexes 4-9 exhibit phosphorescence in solution, in the solid state at room temperature (RT), and also in frozen solvent glasses at 77 K. The emission wavelengths and quantum yields have been found to be highly tunable as a function of the alkynyl ligand. In particular, the trans isomer of complex 9 in a spin-coated film (10 wt % in poly(methyl methacrylate), PMMA) exhibits a high phosphorescence quantum yield of 80 %, which is the highest reported for Pt(II) -based deep-blue emitters. Experimental observations and time-dependent density functional theory (TD-DFT) calculations are strongly indicative of the emission being mainly governed by metal-perturbed interligand ((3) IL) charge transfer.

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trans Bis-N-heterocyclic carbene bis-acetylide palladium(II) complexes

Cited by 8 publications

References 53 publications

Synthesis and Structures of Benzyl‐ and Amido‐Substituted N‐Heterocyclic Palladium Carbene Complexes

Synthesis and Structures of Benzyl‐ and Amido‐Substituted N‐Heterocyclic Palladium Carbene Complexes

N-heterocyclic carbene metal complexes: photoluminescence and applications

Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene Pt^II Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies

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trans Bis-N-heterocyclic carbene bis-acetylide palladium(II) complexes

Cited by 8 publications

References 53 publications

Synthesis and Structures of Benzyl‐ and Amido‐Substituted N‐Heterocyclic Palladium Carbene Complexes

Synthesis and Structures of Benzyl‐ and Amido‐Substituted N‐Heterocyclic Palladium Carbene Complexes

N-heterocyclic carbene metal complexes: photoluminescence and applications

Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene PtII Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies

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Product

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Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene Pt^II Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies