1233573-40-4Relevant academic research and scientific papers
Heterobimetallic PtII-AuI Complexes Comprising Unsymmetrical 1,1-Bis(diphenylphosphanyl)methane Bridges: Synthesis, Photophysical, and Cytotoxic Studies
Shahsavari, Hamid R.,Giménez, Nora,Lalinde, Elena,Moreno, M. Teresa,Fereidoonnezhad, Masood,Babadi Aghakhanpour, Reza,Khatami, Mehri,Kalantari, Foroogh,Jamshidi, Zahra,Mohammadpour, Mozhdeh
, p. 1360 - 1373 (2019)
In the present work, a series of aryl-cycloplatinated(II) complexes with general formula [Pt(C^N)(Ar)(κ1-dppm)], 1, [C^N = 7,8-benzoquinolinyl (bzq) or 2-phenylpyridinyl (ppy); Ar = C6F5 or p-MeC6H4, dppm = 1,1-bis(diphenylphosphanyl)methane] was employed in the reaction with AuCl(SMe2) in order to generate heterobimetallic PtII-AuI complexes, [Pt(C^N)(Ar)(μ-dppm)Au(Cl)], 2, featuring a dppm bridge between the metal centers. The expectation was to induce metallophilic character into the excited state and to reduce non-radiative deactivation pathways of the dangling auxiliary κ1-dppm ligand through molecular motions, to improve the photophysical properties. After characterization of the new complexes by means of NMR spectroscopy and X-ray crystallography technique, the photophysical properties of all the complexes were investigated by UV/Vis and photoluminescence spectroscopy. Both of the monometallic complexes and heterobimetallic products have shown to be luminescent in different states and temperature conditions. However, by addition of AuI, the impact on the photophysics of the heterobimetallic products in relation to the precursors with dangling dppm is minimal, a finding which can be attributed to the absence of a PtII-AuI bond in these compounds. Indeed, the character of the excited states of the monomer PtII complexes and their corresponding bimetallic PtII-AuI ones are similar, as confirmed by density functional theory (DFT) and time resolved DFT (TD-DFT) calculations. The cytotoxic activities of the compounds along with that of [ClAu(μ-dppm)AuCl] were evaluated against human breast cancer (MCF-7), human lung cancer (A549), human ovarian cancer (SKOV3) and non-tumorigenic epithelial breast (MCF-10A) cell lines. The highest activity was found for the heterometallic Pt-Au species, suggesting a cooperative effect of both metallic fragments. The most cytotoxic compound, i.e. [Pt(bzq)(p-MeC6H4)(μ-dppm)Au(Cl)], 2b, effectively causes cell death in MCF-7 cancer cell line by inducing apoptosis. Fluorescence microscopy experiments for 2a were performed.
Comparison of coordination mode of some biphosphine ligands in cyclometalated organoplatinum(II) complexes
Esmaeilbeig, Ahmad R.,Haghighi, Mohsen Golbon,Nikahd, Sahebeh,Hashemi, Sara,Mosarezaee, Mohammad,Rashidi, Mehdi,Nabavizadeh, S. Masoud
supporting information, p. 93 - 100 (2014/03/21)
The reaction of the cyclometalated complexes [PtR(?N)(SMe 2)], 1, in which R is Me or 4-MeC6H4, and ?N is either ppy (deprotonated 2-phenylpyridine) or bhq (deprotonated benzo-h-quinoline), with 1,2-bis[bis(pentafluorophen
Substitution reactions involving cyclometalated platinum(II) complexes: Kinetic investigations
Nabavizadeh, S. Masoud,Shahsavari, Hamid R.,Namdar, Masoud,Rashidi, Mehdi
, p. 3564 - 3571 (2011/10/30)
Substitution reaction of the labile SMe2 ligand in the cyclometalated platinum(II) complexes of general formula [PtAr(ppy)(SMe 2), 1, in which ppy = deprotonated 2-phenylpyridyl and Ar = p-MeC6H4 or p-MeOC6H4, by several N or P donor reagents were studied; the N-donors, N, are pyridine (Py) and substituted pyridines, N = 4-MePy, Py, Py-d5, 2-MePy, 3-PhPy, 3,4-Me2Py, 4-tBuPy or 3-C(O)OMePy, and the P-donors, L, are phosphines or phosphites, L = P(OPh)3, P(O-iPr) 3, PPh3, PPh2Me and L2 = Ph 2PCH2PPh2, bis(diphenylphosphino)methane (dppm). The products were identified by multinuclear NMR studies as [PtAr(ppy)(N), 2, or [PtAr(ppy)(L), 3, respectively. Complexes 1 have a MLCT band in the visible region which was used to easily follow the kinetics of the ligand substitution reactions by UV-vis spectroscopy. Although the complexes 1 contain two cis Pt-C bonds, the substitution reactions followed a normal associative mechanism. The rates of reactions were depended on the concentration and the nature of the entering group. The ΔH?/ ΔS? compensation plot gave a straight line suggesting the operation of the same mechanism for all entering nucleophiles.
