Cyclometalated Platinum(II) Complexes Bearing Bidentate <i>O</i>,<i>O</i>′-Di(alkyl)dithiophosphate Ligands: Photoluminescence and Cytotoxic Properties

Abedanzadeh

et al. 2018

Self Cite

Yield: 76%. Elem. anal. Calcd for C 30 H 44 NPPt (644.73); C, 55.89; H, 6.88; N, 2.17. Found: C, 55.76; H, 6.82; N, 2.26. 1 H NMR (400 MHz, CDCl 3 ): δ = 1.07 (d, 3 J PH = 5.3 Hz, 2 J PtH = 84.5 Hz, 3H, PtMe), 1.20-1.40 (m, 9H, Cy), 1.65 (m, 6H, Cy), 1.70-1.90 (m, 9H, Cy), 1.97-2.14 (m, 6H, Cy), 2.36 (m, 3H, Cy), 7.09 (m, 1H, H 4′ ), 7.16 (t, 1H, 3 J HH = 7.3 Hz, H 5′ ), 7.35 (td, 1H, 3 J HH = 7.3 Hz, 4 J HH = 2.9 Hz, 4 J PtH = 29.7 Hz, H 5 ), 7.70 (bd, 1H, 3 J HH = 7.8, H 4 ), 7.85 (m, 2H, H 3 and H 6′ ), 7.95 (dd, 1H, 3 J HH = 6.3 Hz, 4 J HH = 1.1 Hz, 3 J PtH = 46.8 Hz, H 3′ ), 8.84 (d, 1H, 3 J HH = 5.6 Hz, 3 J PtH = 18.3 Hz, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −15.3 (d, 2 Yield: 81%. Elem. anal. Calcd for C 32 H 44 NPPt (668.75); C, 57.47; H, 6.63; N, 2.09. Found: C, 57.31; H, 6.69; N, 2.21. 1 H NMR (400 MHz, CDCl 3 ): δ = 0.83-2.61 (3H of Me and 33H of Cy), 7.46 (dd, 1H, 3 J HH = 7.9 Hz, 3 J HH = 7.8 Hz, H 8 ), 7.56 (d, 1H, 3 J HH = 8.1 Hz, H 6 ), 7.67 (d, 1H, 3 J HH = 8.1 Hz, H 5 ), 7.74 (m, 1H, H 3 ), 7.82 (d, 1H, 3 J HH = 8.7 Hz, H 7 ), 8.23 (dd, 1H, 3 J HH = 7.1 Hz, 3 J PtH = 45.5 Hz, H 9 ), 8.34 (d, 1H, 3 J HH = 8.3 Hz, H 4 ), 9.15 (d, 1H, 3 J HH = 5.3 Hz, 4 J HH = 1.1 Hz, 3 J PtH = 17.2 Hz, H 2 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −16.0 (d, 2 J PC = 7 Hz, 1 J PtC = 754 Hz, PtMe), 26.6 (s, C of PCy 3 ), 1 H NMR (400 MHz) in CDCl 3 : δ = 0.86-2.11 (39H, aliphatic region, overlapping multiplets of 2Me and 3Cy), 7.21 (m, 1H, 3 J HH = 6.6 Hz, H 4′ ), 7.50 (dd, 2H, 3 J HH = 6.5 Hz, 4 J HH = 2.1 Hz, 4 J PtH = 53.1 Hz, H 5 and H 3′ ), 8.03 (m, 1H, 3 J HH = 7.9 Hz, 3 J HH = 7.8 Hz, H 4 ), 8.22 (d, 1H, 3 J HH = 6.5 Hz, H 5′ ), 10.09 (d, 3 J HH = 5.5 Hz, 4 J PtH = 16.1 Hz, 1H, H 3 ), 10.26 (d, 1H, 3 J HH = 7.83 Hz, 1H, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −7.3 (d, 2 J PC = 4 Hz, 1 J PtC = 624 Hz, PtMe (Me trans to N)), 10.7 (d, 2 J PC = 106 Hz, 1 J PtC = 461 Hz, PtMe (Me trans J PtP = 955 Hz, 1P of PCy 3 ); 195 Pt{ 1 H} NMR (86 MHz, CDCl 3 ): δ = −3215.1 (s, 1 J PtP = 957 Hz, 1Pt). 4.3.2 | cis-[PtMe 2 I(k 2 N,C-ppy)(PCy 3 )] (2a) 1 H NMR (400 MHz) in CDCl 3 : δ = 0.85-2.12 (39H, aliphatic region, overlapping multiplets of 2Me and 3Cy), 7.22 (dd, 3 J HH = 7.8 Hz, 3 J HH = 7.3 Hz, 1H, H 4′ ), 7.33 (m, 2H, H 5′ and H 6′ ), 7.50 (d, 2H, 3 J HH = 7.8 Hz, 4 J PtH = 48.9 Hz, H 3′ ), 7.71 (m, 1H, H 4 ), 7.87 (ddd, 3 J HH = 7.5 Hz, 3 J HH = 8.0 Hz, 4 J HH = 1.3 Hz, 1H, H 5 ), 7.96 (d, 1H, 3 J HH = 8.1 Hz, H 3 ), 10.12 (d, 1H, 3 J HH = 14.8 Hz, H 6 ); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ = −7.3 (d, 2 J PC = 3 Hz, 1 J PtC = 670 Hz, PtMe (Me trans to N)), 10.4 (d, 2 J PC = 109 Hz, 1 J PtC = 469 Hz, PtMe (Me trans to P)), 26.4 (s, C of PCy 3 ), 27.9 (d, 3 J PC = 10 Hz, C of

Section: Introductionmentioning

confidence: 99%

Carbon‐iodide bond activation by cyclometalated Pt (II) complexes bearing tricyclohexylphosphine ligand: A comparative kinetic study and theoretical elucidation

Chamyani

Abedanzadeh

et al. 2018

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“…Standard 3‐(4,5‐dimethylthiazol‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay was used for assessing cytotoxic activities of 1 and 2 according to a known protocol . The cells were harvested and plated in 96‐well microplates at a density of 1 × 10 4 cells per well in 100 μl of complete culture medium.…”

Section: Methodsmentioning

confidence: 99%

(Benzyl isocyanide)gold(I) pyrimidine‐2‐thiolate complex: Synthesis and biological activity

Fereidoonnezhad

Lotfi

et al. 2018

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The reaction of [(Me2S)AuCl] with an equimolar amount of benzyl isocyanide (PhCH2NC) ligand led to the formation of complex [(PhCH2NC)AuCl] (1). The solid‐state structure of 1 was determined using the X‐ray diffraction method. Through a salt metathesis reaction, the chloride ligand in 1 was replaced by pyrimidine‐2‐thiolate (SpyN−) to afford the complex [(PhCH2NC)Au(η1‐S‐Spy)] (2), which was characterized spectroscopically. The cytotoxic activities of 1 and 2 were evaluated against three human cancer cell lines: ovarian carcinoma (SKOV3), lung carcinoma (A549) and breast carcinoma (MCF‐7). Complex 2 showed higher cytotoxicity than cisplatin against SKOV3 and MCF‐7 cancer cell lines. It showed a strong anti‐proliferative activity with IC50 of 7.80, 6.26 and 6.14 μM, compared with that measured for cisplatin which was 7.62, 12.36 and 11.47 μM, against A549, SKOV3 and MCF‐7 cell lines, respectively. The induction of cellular apoptosis by 2 was also studied on MCF‐7 cell line. Our results indicated that 2 could induce apoptosis in cancerous cells in a dose‐dependent manner.

“…In the study presented here, based on our previous experiences in the field of luminescent cycloplatinated(II) complexes, we investigated in depth a series of dinuclear cycloplatinated(II) complexes containing different C^N cyclometalated ligands, and dppm or dppa as a linker between the two cycloplatinated(II) parts. A deep orange or red emission is observed for all cases in the solid state at 298 and 77 K. Also, all the complexes are emissive in solution at 298 K and glassy state.…”

Section: Introductionmentioning

confidence: 99%

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

Nazari

2019

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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).