Green–Blue Emitters: NHC‐Based Cyclometalated [Pt(C^C*)(acac)] Complexes

Unger, Yvonne; Meyer, Dirk C.; Molt, Oliver; Schildknecht, Christian; Münster, Ingo; Wagenblast, Gerhard; Straßner, Thomas

doi:10.1002/anie.201001316

Cited by 234 publications

(277 citation statements)

References 13 publications

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“…For the rest of the crystals, the absorption correction was performed using XABS2 109 (3,6) or MULTI-SCAN 110 (9), with the WINGX program suite. 111 The structures were solved by direct and Patterson methods using SIR2004 112 (1) or DIRDIF96 113 (3,6,7,8,11) or by direct methods using SHELXS-97 114 (9) and refined by fullmatrix least-squares on F 2 with SHELXL-97. 114 All non-hydrogen atoms were assigned anisotropic displacement parameters.…”

Section: ' Introductionmentioning

confidence: 99%

Luminescent Cycloplatinated Complexes Containing Poly(pyrazolyl)-borate and -methane Ligands

et al. 2011

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Cycloplatinated neutral [Pt(C ∧ N){H 2 B(pz) 2 }] (1À3) [C ∧ N = benzoquinolate (bzq), 2-phenylpyridinate (ppy), and 2-phenylquinolate (pq)] and [Pt(pq){HB(pz) 3 }] 10 and cationic [Pt(C ∧ N){H 2 C(pz) 2 }] + (4À6) and [Pt(C ∧ N){HC(pz) 3 }] + (7À9)complexes were synthesized by the reaction of the corresponding precursors [Pt(C ∧ N)(μ-Cl)] 2 with the adequate poly-(pyrazolyl)-borate or -methane ligand. However, the reactions of [Pt(C ∧ N)(μ-Cl)] 2 (C ∧ N = bzq, ppy) with [HB(pz) 3 ] À evolve with BÀN bond cleavage, yielding the binuclear systems [Pt(C ∧ N)(μ-pz)] 2 as a mixture of cis and trans isomers. Complexes were characterized in solution by multinuclear and multidimensional NMR spectroscopy. The solid-state structures of 1, 3, 6, 7À9, and [Pt(bzq)(μ-pz)] 2 were confirmed by X-ray single-crystal studies. The absorption, emission, and electrochemical properties of these complexes are mainly dominated by the nature of the cyclometalated ligand and the charge of the complex. On the basis of TD-DFT calculations (1, 7À9), the lowest-energy absorption for neutral 1 has been ascribed to a mixed 1 ILCT/ 1 MLCT transition, whereas for the cationic 7À9, it is mainly attributed to 1 ILCT combined with some CT to both ligands in 9 ( 1 MLCT/ML 0 CT 9) or to the HC(pz) 3 in 7 and 8 ( 1 ML 0 CT). These compounds are emissive in all media (except 4 and 10 in the solid state at 298 K). In the solid state at 298 K and at 77 K, these complexes display intense phosphorescence, which is typical of monomers. In deoxygenated CH 3 CN solutions at 298 K, phosphorescence is accompanied by higher-energy fluorescence in complexes 1, 4, and 8, which disappears at concentrated solutions and at 77 K. Complex 7 displays a special behavior, observing fluorescence and/or excimer fluorescence only at 298 K and excimeric emission (diluted glasses) and emission from aggregates in concentrated glasses. TD-DFT of the lowest-lying excited states responsible for the phosphorescence of 1 and 7À9 reveals a 3 ILCT origin with a mixed 3 MLCT character for 1 and, in the case of the cationic 7À9, a 3 ILCT transition mixed with 3 ML 0 CT (especially in 8) and with some 3 MLCT in 9. ' INTRODUCTIONCyclometalated square-planar platinum(II) complexes have attracted great interest in recent years due to their luminescent properties 1À12 with potential applications in optoelectronic devices, 2,3,7,10,11,13À25 photocatalysts, 26 and chemical or biochemical sensors. 27À31 Emission from these Pt(II) complexes is typically assigned to ligand-centered ( 3 LC) and/or metal-to-ligand charge-transfer ( 3 MLCT) states, although some degree of ligand-to-ligand 0 charge-transfer ( 3 LL 0 CT) states is also possible. Additionally, the square-planar nature of these complexes facilitates the formation of dimers or aggregates through noncovalent π 3 3 3 π and/or Pt 3 3 3 Pt interplanar stacking interactions, both in the solid state and in solution. 32À44 As a consequence, they exhibit rich photophysical behavior causing a marked red shift relative to the mononuclear emissio...

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Section: ' Introductionmentioning

confidence: 99%

Luminescent Cycloplatinated Complexes Containing Poly(pyrazolyl)-borate and -methane Ligands

et al. 2011

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“…It is worth noting that a similar reaction between [Pt 2 (m-Cl) 2 (ppy) 2 ] (ppy ¼ metalated 2-phenylpyridine) with Pb(Spy) 2 readily yields a platinum(III) complex [Pt 2 Cl 2 (Spy) 2 (ppy) 2 ] [18]. The NMR spectra ( 1 H, 13 The complex 2 may exist in different geometrical and optical configurations. In case of geometrical configurations cis and trans isomers are possible [34] (Supplementary information, Fig.…”

Section: Synthesis and Spectroscopymentioning

confidence: 98%

“…Anal. calcd for C 13 To a freshly prepared methanolic solution (5 mL) of NaSeCH 2 CH 2 NMe 2 (prepared from (SeCH 2 CH 2 NMe 2 ) 2 (0.147 g, 0.486 mmol) and solid NaBH 4 (0.040 g, 1.057 mmol)) was added [Pt 2 (m-Cl) 2 (C 8 H 12 OMe) 2 ] (0.357 g, 0.482 mmol). The reaction mixture was stirred for 2 h. The solvent was evaporated to dryness and the residual solid was extracted with dichloromethane (3 Â 10 mL) to yield a pale yellow solid 7 (0.385 g, 0.793 mmol, 82%), m.p.…”

Section: Synthesis Of [Pt(s 2 P{opr I } 2 ) 2 ] (5)mentioning

confidence: 99%

“…Mass spectra were recorded on a Waters Q-TOF micro (YA-105) time of flight mass spectrometer. 1 H,13 C{ 1 H}, 31 P{ 1 H}, 77 Se{ 1 H} and 195 Pt{ 1 H} NMR spectra were recorded on a Bruker Avance II-300 NMR spectrometer operating at 300, 75.47, 121.5, 57.24 and 64.29 MHz, respectively. Chemical shifts are relative to internal chloroform peak (d 7.26 1 H and 77.0 for 13 C), external Me 2 Se for 77 Se{ 1 H} (secondary reference Ph 2 Se 2 in CDCl 3 d 463 ppm) and Na 2 PtCl 6 in D 2 O for 195 Pt{ 1 H}.…”

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confidence: 99%

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Syntheses of platinum(II) complexes of cyclo-octenyl group and isolation of a self-assembled oxo-bridged macrocyclic complex [Pt4(Spy)4(C8H12-O-C8H12)2]

Ghavale

Dey

Wadawale

et al. 2011

Journal of Organometallic Chemistry

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“…발광 착체들의 중심금속으로는 이리듐(III)이 많이 사용되고 있지만, 백금(II)착체에 대한 관심도 증가하고 있다 [11]. 백금의 경우, 단파장(400~500 nm)에서의 발광특성이 보고되어 있고 결합된 배위 자의 종류에 따라서 발광파장이 이동되는 것이 보고되었다 [13][14][15][16].…”

Section: 서 론unclassified

A Synthesis and Characterization of Pt(II) Complexes with Bipyrimidin-based Back-bone System

Son¹,

Ahn²,

Chung³

2016

Korean Chemical Engineering Research

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Green–Blue Emitters: NHC‐Based Cyclometalated [Pt(C^C*)(acac)] Complexes

Cited by 234 publications

References 13 publications

Luminescent Cycloplatinated Complexes Containing Poly(pyrazolyl)-borate and -methane Ligands

Luminescent Cycloplatinated Complexes Containing Poly(pyrazolyl)-borate and -methane Ligands

Syntheses of platinum(II) complexes of cyclo-octenyl group and isolation of a self-assembled oxo-bridged macrocyclic complex [Pt4(Spy)4(C8H12-O-C8H12)2]

A Synthesis and Characterization of Pt(II) Complexes with Bipyrimidin-based Back-bone System

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