Assembly of Symmetrical or Unsymmetrical Cyclometalated Organoplatinum Complexes through a Bridging Diphosphine Ligand

Nabavizadeh, S. Masoud; Haghighi, Mohsen Golbon; Esmaeilbeig, Ahmad R.; Raoof, Fatemeh; Mandegani, Zeinab; Jamali, Sirous; Rashidi, Mehdi; Puddephatt, Richard J.

doi:10.1021/om100295q

Cited by 52 publications

(46 citation statements)

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“…These known complexes with general formula [Pt(p-MeC 6 H 4 )(C^N)(SMe 2 )], in which C^N= benzo[h]quinolate (bzq), 1, or 2-phenylpyridinate (ppy), 2, have been characterized by NMR spectroscopy and X-ray crystallography. 33,34 Crystal packing of the complex 1 (see Figure 1) reveals that the 4 molecules are stacked through π-π* interaction of the planar bzq groups with an interplanar distance of 3.3 Å, while the complex 2 failed to show such an interaction. This kind of π-π* interaction can cause excimer formation affecting on emission property of complex 2.…”

Section: Resultsmentioning

confidence: 99%

“…Therefore emission in the complexes is probably due to a mixed 3 IL/ 3 MLCT with some 3 L´LCT character. 34 Purities of the synthesized complexes were checked by 1 H NMR and elemental analysis.…”

Section: Computational Studymentioning

confidence: 99%

“…29,30 Generally, expanding of the π-conjugated system causes reduction of the π-π* energy gap leading to red shift in emission energy, 22,26,27,31 although a blue shift behavior may be observed in some cases. 16 We have recently synthesized a series of Pt complexes containing different cyclometalated ligands [32][33][34] and investigated their chemistry in oxidative addition reactions, [35][36][37][38][39] ligand substitution reactions, 40,41 and metal-carbon bond protonolysis. 42 We now report photophysical properties of some cycloplatinated(II) complexes with the general formula [Pt(p-MeC 6 H 4 )(C^N)(SMe 2 )], in which C^N= benzo[h]quinolate (bzq), 1, or 2-phenylpyridinate (ppy), 2), with bzq having an expanded π-system as compared to that in ppy giving novel luminescence properties.…”

Section: Introductionmentioning

confidence: 99%

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Photophysical and DFT studies on cycloplatinated complexes: modification in luminescence properties by expanding of π-conjugated systems

et al. 2015

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To investigate the factors influencing the luminescent properties of cycloplatinated complexes containing aryl and SMe 2 ligands, a detailed study of the photophysical and structural properties of the complexes [Pt(p-MeC 6 H 4 )(C^N)(SMe 2 )], (C^N= benzo[h]quinolate (bzq), 1, or 2-phenylpyridinate (ppy), 2), was conducted in solution and solid state at different temperatures. Density functional theory (DFT) and Time-dependent density functional theory (TD-DFT) investigations were carried out on both the singlet (S 0 , ground) and triplet (T 1 , excited) states of these complexes for explanation of the electronic structures, absorption and emission spectra. In the solid state, these complexes display an intense phosphorescence emission which was red-shifted from 2 to 1 due to expanding of π conjugated system in cyclometalated bzq ligand. These complexes are strongly emissive in 77 K, giving emission peaks similar to those observed at ambient temperature. The complex 1 in deoxygenated CH 2 Cl 2 solution (at low concentration) gave a phosphorescence band which 2 was accompanied by a higher-energy fluorescence band (ascribed to 1 LC transition, centered on bzq ligand), and these bands were disappeared when a concentrated solution or glassy state (77 K) of the complex is in use. On the basis of theoretical calculations, the HOMO level is a mixture of platinum center and ligand orbitals, while the LUMO level is predominantly C^N ligand based. Lowest-lying excited state responsible for the phosphorescence emission (with a significantly long lifetime) is originated from mixed 3 ILCT/ 3 MLCT with some 3 L'LCT excited state and the emission is red shifted to corresponding free cyclometallating ligand.

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Section: Resultsmentioning

confidence: 99%

Section: Computational Studymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photophysical and DFT studies on cycloplatinated complexes: modification in luminescence properties by expanding of π-conjugated systems

et al. 2015

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“…Other diarylplatinum(II) compounds such as [PtAr 2 (SMe 2 ) 2 ] (Ar = 4-MeC 6 H 4 ; 4-MeOC 6 H 4 ) have been shown to be efficient metallation agents in front of 2-phenylpyridine or benzo[h]quinoline ligands, and the assembly of the resulting cyclometallated organoplatinum complexes through bridging diphosphine ligands has been reported (see Scheme 3) [51,52].…”

Section: Activation Of C-h Bonds At Diarylplatinum(ii) Precursorsmentioning

confidence: 99%

“…Scheme 3. Synthesis and assembly of cyclometallated platinum compounds containing aryl ligands [51,52].…”

Section: Activation Of C-h Bonds At Diarylplatinum(ii) Precursorsmentioning

confidence: 99%

Diarylplatinum(II) Compounds as Versatile Metallating Agents in the Synthesis of Cyclometallated Platinum Compounds with N-Donor Ligands

Crespo

2014

Inorganics

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This review deals with the reactions of diarylplatinum(II) complexes with N-donor ligands to produce a variety of cycloplatinated compounds including endo-five-, endo-seven-, endo-six-or exo-five-membered platinacycles. The observed reactions result from a series of oxidative addition/reductive elimination processes taking place at platinum(II)/platinum(IV) species and involving C-X (X = H, Cl, Br) bond activation, arene elimination, and, in some cases, C aryl -C aryl bond formation.

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Synthesis and cytostatic activity of Pt(II) complexes of intramolecularly coordinated phosphine and stibine ligands

Řezníček

Dostál

Růžička

et al. 2012

Applied Organom Chemis

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H 3 ]SbPh 2 }PtCl 2 (6) as the result of different ability of the starting compounds 1-3 to complex platinum centre. Compounds 1-6 were characterized by 1 H, 13 C and 31 P NMR spectroscopy and electrospray ionization mass spectrometry, and molecular structures of 3-6 were determined by X-ray diffraction analysis. The substitution reactions of complexes 4-6 were also studied. The reaction of 5 and 6 with NaI yielded complexes {[2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ]PPh 2 }PtI 2 (7) and {[2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ]SbPh 2 }PtI 2 (8), while the same reaction of 4 with NaI did not proceed. As the compounds 7 and 8 structurally resemble cisplatin, complex {{[2-(Me 2 NCH 2 )-6-(Me 2 NHCH 2 )C 6 H 3 ]PPh 2 }PtCl 2 } + Cl À (9) was prepared as water-soluble platinum complex. The cytotoxic effect of complex 9 was evaluated on human T-lymphocytic leukemia cells MOLT-4 (IC 50 = 27.6 AE 1.8 mmol l À1 ) and human promyelocytic leukemia HL-60 (IC 50 = 55.9 AE 4.9 mmol l À1 ).

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Assembly of Symmetrical or Unsymmetrical Cyclometalated Organoplatinum Complexes through a Bridging Diphosphine Ligand

Cited by 52 publications

References 56 publications

Photophysical and DFT studies on cycloplatinated complexes: modification in luminescence properties by expanding of π-conjugated systems

Photophysical and DFT studies on cycloplatinated complexes: modification in luminescence properties by expanding of π-conjugated systems

Diarylplatinum(II) Compounds as Versatile Metallating Agents in the Synthesis of Cyclometallated Platinum Compounds with N-Donor Ligands

Synthesis and cytostatic activity of Pt(II) complexes of intramolecularly coordinated phosphine and stibine ligands

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