[Pt(topy)(Htopy)(ONO₂)] complex (Htopy = 2‐p‐tolylpyridine) and its analogs: ¹⁹⁵Pt NMR spectra and fabrication of light‐emitting devices

Abstract

We report fast, high-yield syntheses of a series of [Pt(C ∧ N)(HC ∧ N)X] complexes, where HC ∧ N is 2-phenylpyridine (Hppy) or 2-p-tolylpyridine (Htopy) and X − is Cl − , Br − , I − , ONO 2 − , NO 2 − or SCN − . The structure of [Pt(topy)(Htopy)(ONO 2 )] was analyzed by single-crystal X-ray diffraction. Substitution of Cl − with Br − or I − in our complexes shifted the 195 Pt NMR peaks upfield in the order Cl − < Br − < I − , but the magnitudes of their shifts were one-tenth those observed for non-cyclometalated platinum(II) complexes. As the two nitrato complexes showed strong emissions in acetonitrile solution -three to six times those of other complexes -they were used to fabricate OLEDs. Although their emissions were not particularly strong, devices fabricated with platinum(II) complexes containing bulky ligands emitted green light with a short lifetime (τ ).

1H, 13C, 15N and 195Pt NMR studies of Au(III) and Pt(II) chloride organometallics with 2‐phenylpyridine

“…[43 -46] The other pyridine protons in [Au(2ppy 3 or CD 2 Cl 2 , especially in case of the two high-frequency signals (9.50-9.62 and 9.15-9.24 ppm) and the one at the lowest frequency (6.10-6.20 ppm); [2,5,9,17 -19] they were already assigned by Niedermair, Mdleleni and Fukuda et al as H (6) * , H(6) and H(3 ) * , respectively [5,18,19] (see footnote (b) under Table 1). We have found the following order of 1 H peaks, based on the 1 H-13 C and 1 H-15 N HSQC or HMBC spectra :…”

“…[40] The same dependency can be found (Table S3, Supporting Information) for [Pt(3-hexyloxy-2ppy * )(3-hexyloxy-2ppy)Cl] ( H(6) * coord = 1.05 ppm versus H(6) coord = 0.50 ppm), [18] [Pt(2-(4-methylphenyl)-py * )(2-(4-methylphenyl)-py)Cl] ( H(6) * coord = 0.93 ppm versus H(6) coord = 0.58 ppm), [19] [Pt(2-(4-methoxyphenyl)-py * )(2-(4-methoxyphenyl)-py)Cl] ( H(6) * coord = 0.74 ppm versus H(6) coord = 0.44 ppm), [17] [5,9,17,20,21] H(6) * coord = 1.22 ppm for [Pt(2ppy * )(P(C 6 H 5 ) 3 )Cl]; [22] H(6) * coord = 0.73-0.79 ppm for [Pt(2ppy * )(CN) 2 ] − . [14,23] In contrast, when chlorides were absent, the coordination effects were of variable sign and magnitude: [26 -28] H(6) * coord = −0.56 ppm for [Pt(2ppy * ) (P(C 6 H 5 ) 3 )(CH 3 )]; [29] H(6) * coord = 1.00-1.12 ppm for trans…”

“…[13,32] However, the respective 1 H and 13 C signals usually remained unassigned or were assigned inconsistently by various authors. The 195 Pt NMR spectra were described for cis-[Pt(2ppy * ) 2 ] [32 -35] and [Pt(2ppy * )(2ppy)X] (X = Cl, Br, I, SCN, ONO 2 , NO 2 ), [19] while those of 15 [36] while trans(N,N)-[Pt(2ppy * )(2ppy)Cl] and trans(S,N)-[Pt(2ppy * )(DMSO-d 6 )Cl] exhibit high cytotoxicity. [6,22,37,38] Experimental Materials 2-Phenylpyridine (2ppy, 98% purity) was purchased from Aldrich, while Pt (99.9%) and Au (99.99%) were from the Polish State Mint.…”

“…[1] but entirely different from the suggestions of Fan et al [3] or Parish et al [15] The presence of eight proton signals corresponds well to the results of single-crystal X-ray studies for solid [Au(2ppy * )Cl 2 ] (IJAQEP [3] ), suggesting the preservation of its structure in DMSOd 6 [18] Fukuda et al (in CDCl 3 ): 9.62-H(6) * ( 3 J HPt = 18 Hz), 9.24-H(6) ( 3 J HPt = 20 Hz), 6.19-H(3 ) * ( 3 J HPt = 16 Hz). [19] c Formed in situ by dissolving [Pt(2ppy…”

“…[Au(2ppy * [3] trans(S,N)-[Au(2ppy * )(SCN)(NCS)] -ILETOI; [7] trans(C,N)-[Au(2ppy * )(CH 2 COCH 3 )Cl] -BIGRAL and trans(C,N)-[Au(2ppy * ) (CH 2 COCH 3 )(ONO 2 )] -BIGREP; [8] [9] [Pt(2ppy * )(NH 2 CH 2 CH 2 NH 2 )]Cl -ZUDGIO; [4] trans(C,N)-[Pt(2ppy * ) (DMSO)(CH 3 )] -BEZPEC; [10] trans(C,N)-[Pt(2ppy * )(DMSO)(C 6 H 5 )] -TICSII and trans(C,N)-[Pt(2ppy * )(DMSO) (3,5-dimethylphenyl)] -TICSEE; [11] trans(N,N)-[Pt(2ppy * )(8-oxyquinolinate)] -WESQUH; [12] cis-[Pt(2ppy * ) 2 ] -CULWUB; [13] K[Pt(2ppy * )(CN) 2 ]· 2(CH 3 COC H 3 ). [14] These or similar compounds were also investigated by 1 H and/or 13 C NMR methods: [Au(2ppy * )Cl 2 ]; [1,3,15] [Au(2ppy * ) (OCOCH 3 [3] [Au(2ppy * )(SC H 2 CH 2 S)] and [Au(2ppy * )(SCH 2 CH 2 NH 2 )] + ; [15] trans(S,N)-[Au(2p py * )(SCN)(NCS)]; [7] trans(C,N)-[Au(2ppy * )(CH 2 COCH 3 )(ONO 2 )]; [8] [Au(2ppy * )(NH 2 CH 2 CH 2 NH 2 )] 2+ and [Au(2ppy * )(2,2 -bipyridine )] 2+ ; [16] trans(N,N)-[Pt(2ppy * )(2ppy)Cl]; [2,5,9,17 -19] [Pt(2ppy * )(2ppy) X] (X = Br, I, SCN, ONO 2 , NO 2 ); [19] [Pt(2ppy * )Cl 2 ] − ; [2] [Pt(2ppy * ) (CO)Cl]; [5,17,20] [Pt(2ppy * )(NH 3 )Cl]; [17] trans(S,N)-[Pt(2ppy * )(DMSO) Cl]; [9,17,21] [Pt(2ppy * )(P(C 6 H 5 ) 3 )Cl] and [Pt(2ppy * )(py)Cl]; [22] [Pt(2p py * )(CN) 2 ] − ; [14,23] [Pt(2ppy * )(2,4-pentanedionate)], [Pt(2ppy * )(1,1, 1,5,5,5-hexafluoro-2,4-pentanedionate)], [Pt(2ppy * )(2,2,6,6-tetramethyl-3,5-heptanedionate)] and [Pt(2ppy * )(benzoylacetonate )]; [21,...…”