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Synthesis, characterization, and photophysical properties of three platinum(II) complexes bearing fluorescent analogues of the Di-2-pyridylmethane ligand.

ABSTRACT: Three new ligands of the general formula [RNHCH(py)(2)] (py = pyridine; R = tosyl, Ts-dpm; R = dansyl, Ds-dpm; R = 7-nitro-1,2,3-benzoxadiazole, NBD-dpm) have been synthesized and characterized. Reactions of these ligands with cis-[Pt(DMSO)(2)Cl(2)] (DMSO = dimethyl sulfoxide) in methanol affords [Pt(Ts-dpm)Cl(2)] (1), [Pt(Ds-dpm)Cl(2)] (2), and [Pt(NBD-dpm)Cl(2)] (3). The crystal structures of these complexes reveal bidentate coordination of the ligands to the Pt center with nonplanar chelate rings. Because of inequivalent substituents on the methine carbon atom of the ligands, distinct exo and endo isomers exist in the three complexes. X-ray analyses indicate that 1 crystallizes in the endo conformation, 2 in the exo conformation, and 3 as a mixture of the two conformers. The (1)H NMR and (195)Pt NMR spectra of the complexes display two sets of independent signals corresponding to the chemically inequivalent exo and endo conformers. The exo conformer was determined by 2D NMR spectroscopy to be thermodynamically favored for all three complexes. Density functional theory (DFT), time-dependent DFT, and atoms in molecules calculations were carried out for both conformers of 3 to investigate differences in their electronic structures and to explore intramolecular interactions. In the presence of dioxygen, 1 thermally decomposes at 60 degrees C to form several unidentified products. Compound 2 is thermally stable even in the presence of dioxygen and water but upon light exposure decomposes to form a new platinum(II) species with a (195)Pt NMR shift of -2177 ppm. Compound 3 reacts both thermally and photochemically in the presence of dioxygen and trace amounts of water to form both 4-amino-7-nitro-2,1,3-benzoxadiazole and [Pt(dpk)Cl(2)] (dpk = di-2-pyridyl ketone). Oxidation of 1 and 3 with H(2)O(2) in acetic acid affords a mixture of compounds, two of which contain dpm ligands bound in a tridentate manner to platinum.

SUBMITTER: Wilson JJ

PROVIDER: S-EPMC2879454 | biostudies-literature | 2010 Jun

REPOSITORIES: biostudies-literature

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Synthesis, characterization, and photophysical properties of three platinum(II) complexes bearing fluorescent analogues of the Di-2-pyridylmethane ligand.

Wilson Justin J JJ Fedoce Lopes Juliana J Lippard Stephen J SJ

Inorganic chemistry 20100601 11

Three new ligands of the general formula [RNHCH(py)(2)] (py = pyridine; R = tosyl, Ts-dpm; R = dansyl, Ds-dpm; R = 7-nitro-1,2,3-benzoxadiazole, NBD-dpm) have been synthesized and characterized. Reactions of these ligands with cis-[Pt(DMSO)(2)Cl(2)] (DMSO = dimethyl sulfoxide) in methanol affords [Pt(Ts-dpm)Cl(2)] (1), [Pt(Ds-dpm)Cl(2)] (2), and [Pt(NBD-dpm)Cl(2)] (3). The crystal structures of these complexes reveal bidentate coordination of the ligands to the Pt center with nonplanar chelate r ...[more]

PMID: 20423108

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Project description:The luminescent, mono-diimine ruthenium complexes [(H)Ru(CO)(PPh3)2(dcbpy)][PF6] (1) (dcbpy = 4,4'-dicarboxy-2,2'-bipyridyl) and [(H)Ru(CO)(dppene)(5-amino-1,10-phen)][PF6] (2) (dppene = bis(diphenylphosphino)ethylene; phen = phenanthroline) were conjugated with 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine (DPPE) and with cholesterol in the case of complex 2. Using standard conjugation techniques, compound 1 gives the bis-lipid derivative [(H)Ru(CO)(PPh3)2(dcbpy-N-DPPE2)][PF6] (3), while 2 provides the monolipid conjugate [(H)Ru(CO)(dppene)(1,10-phen-5-NHC(S)-N-DPPE)][PF6] (4) and the cholesterol derivative [(H)Ru(CO)(dppene)(1,10-phen-5-NHC(O)Ocholesteryl)][PF6] (5). These compounds were characterized by spectroscopic methods, and their photophysical properties were measured in organic solvents. The luminescence of lipid conjugates 3 and 4 is quenched in organic solvents while compound 4 shows a weak, short-lived, blue-shifted emission in aqueous solution. The cholesterol conjugate 5 shows the long-lived, microsecond-time scale emission associated with triplet metal-to-ligand charge-transfer excited states. Incorporation of conjugate 3 in lipid bilayer vesicles restores the luminescence, but with blue shifts (~80 nm) accompanied by nanosecond-time scale lifetimes. In the vesicles conjugate 4 shows a short-lived and blue-shifted emission similar to that observed in solution but with increased intensity. Conjugation of the complex [(H)Ru(CO)(PhP2C2H4C(O)O-N-succinimidyl)2(bpy)][PF6] (6") (bpy = 2,2'-bipyridyl) with DPPE gives the phosphine-conjugated complex [(H)Ru(CO)(PhP2C2H4C(O)-N-DPPE)2(bpy)][PF6] (7). Complex 7 also exhibits a short-lived and blue-shifted emission in solution and in vesicles as observed for complexes 3 and 4. We have also conjugated the complex [Ru(bpy)2(5-amino-1,10-phen)][PF6]2 (8) with both cholesterol (9) and DPPE (10). Neither complex 9 nor the previously reported complex 10 exhibited the blue shifts observed for complexes 3 and 4 when incorporated into large unilamellar vesicles (LUVs). The anisotropies of the emissions of complexes 3, 4, and 7 were also measured in LUVs, and those of complex 5 were measured in both glycerol and LUVs. High fundamental anisotropies were observed for complexes 3, 4, and 7.

Project description:A new family of cyclometalated ruthenium(II) complexes [Ru(N^N)2(C^N)]+ derived from the ?-extended benzo[h]imidazo[4,5-f]quinolone ligand appended with thienyl groups (n = 1-4, compounds 1-4) was prepared and its members were characterized for their chemical, photophysical, and photobiological properties. The lipophilicities of 1-4, determined as octanol-water partition coefficients (log Po/w), were positive and increased with the number of thienyl units. The absorption and emission bands of the C^N compounds were red-shifted by up to 200 nm relative to the analogous Ru(II) diimine systems. All of the complexes exhibited dual emission with the intraligand fluorescence (1IL, C^N-based) shifting to lower energies with increasing n and the metal-to-ligand charge transfer phosphorescence (3MLCT, N^N-based) remaining unchanged. Compounds 1-3 exhibited excited state absorption (ESA) profiles consistent with lowest-lying 3MLCT states when probed by nanosecond transient absorption (TA) spectroscopy with 532 nm excitation and had contributions from 1IL(C^N) states with 355 nm excitation. These assignments were supported by the lifetimes observed (<10 ns for the 1IL states and around 20 ns for the 3MLCT states) as well as a noticeable ESA for 3 with 355 nm excitation that did not occur with 532 nm excitation. Compound 4 was the only member of the family with two 3MLCT emissive lifetimes (15, 110 ns), and the TA spectra collected with both 355 and 532 nm excitation was assigned to the 3IL state, which was corroborated by its 4-6 ?s lifetime. The ESA for 4 had a rise time of approximately 10 ns and an initial decay of 110 ns, which suggests a possible 3MLCT-3IL excited state equilibrium that results in delayed emission from the 3MLCT state. Compound 4 was nontoxic toward human skin melanoma cells (SKMEL28) in the dark (EC50 = >300 ?M); 1-3 were cytotoxic and yielded EC50 values between 1 and 20 ?M. The photocytotoxicites with visible light ranged from 87 nM with a phototherapeutic index (PI) of 13 for 1 to approximately 1 ?M (PI = >267) for 4. With red light, EC50 values varied from 270 nM (PI = 21) for 3 to 12 ?M for 4 (PI = >25). The larger PIs for 4, especially with visible light, were attributed to the much lower dark cytotoxicity for this compound. Because the dark cytotoxicity contributes substantially to the observed photocytotoxicity for 1-3, it was not possible to assess whether the 3IL state of 4 led to a much more potent phototoxic mechanism in the absence of dark toxicity. There was no stark contrast in cellular uptake and accumulation by laser scanning confocal and differential interference contrast microscopy to explain the large differences in dark toxicities between 1-3 and 4. Nevertheless, the study highlights a new family of Ru(II) C^N complexes where ?-conjugation beyond a certain point results in low dark cytotoxicity with high photocytotoxicity, opposing the notion that cyclometalated Ru(II) systems are too toxic to be phototherapeutic agents.

Dataset Information

Synthesis, characterization, and photophysical properties of three platinum(II) complexes bearing fluorescent analogues of the Di-2-pyridylmethane ligand.

Publications

Synthesis, characterization, and photophysical properties of three platinum(II) complexes bearing fluorescent analogues of the Di-2-pyridylmethane ligand.

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