RESUMEN
(ClImDipp)P-P(Dipp)Ë (1Ë), a rare example of a neutral, mixed substituted diphosphene radical, has been prepared by reduction of (ClImDipp)PP(Dipp)[OTf] (2[OTf]) and (ClImDipp)PP(Cl)(Dipp) (3) with cobaltocene (CoCp2) (ClImDipp = 4,5-dichloro-1,3-bis(1,3-diisopropylphenyl)-imidazol-2-yl, Dipp = 2,6-diisopropylphenyl). Radical compound 1Ë readily activates white phosphorus (P4), resulting in the formation of an intriguing octaphosphane butterfly compound P8(ClImDipp)2(Dipp)2 (4).
RESUMEN
We present a straightforward one-step process to access a range of novel p-diindolepyrazines via an unprecedented [n-Bu4N][Fe(CO)3(NO)] (TBA[Fe])-catalyzed intermolecular nitrogenative dimerization of various indole derivatives. Remarkably, tosylazide functions as a N1-synthon forming the central pyrazine unit that joins the two indole subunits. The catalytic transformation shows a good substrate scope, and the obtained products show interesting electronic properties.
RESUMEN
Two series of regioisomeric dicyanomethylene substituted dithienodiazatetracenes with formal para- or ortho-quinodimethane subunits were synthesized and characterized. Whereas the para-isomers (p-n, diradical index y0 =0.01) are stable and isolable, the ortho-isomer (y0 =0.98) dimerizes into a covalent azaacene cage. Four elongated σ-CC bonds are formed and the former triisopropylsilyl(TIPS) -ethynylene groups transformed into cumulene units. The azaacene cage dimer (o-1)2 was characterized by X-ray single crystal structure analysis and temperature-dependent infrared (IR), electron paramagnetic resonance (EPR, solid-state), nuclear magnetic resonance (NMR) and ultraviolet-visible (UV/Vis) spectroscopies (solution) indicating reformation of o-1.
RESUMEN
Mixed-valence (MV) binuclear ferrocenyl compounds have long been studied as models for testing theories of electron transfer and in attempts to design molecular-scale electronic devices (e.g., molecular wires). In contrary to that, far less attention has been paid to MV binuclear ferrocenes as anticancer agents. Herein, we discuss the synthesis of six 1,2,3-triazole ferrocenyl compounds for combined (spectro)electrochemical, electron paramagnetic resonance (EPR), computational, and anticancer activity studies. Our synthetic approach was based on the copper-catalyzed 1,3-dipolar azide-alkyne cycloaddition reaction and enabled us to obtain in one step compounds bearing either one, two, or three ferrocenyl entities linked to the common 1,2,3-triazole core. Thus, two series of complexes were obtained, which pertain to derivatives of 3'-azido-3'-deoxythymidine (AZT) and 3-azidopropionylferrocene, respectively. Based on the experimental and theoretical data, the two mono-oxidized species corresponding to binuclear AZT and trinuclear 3-azidopropionylferrocene complexes have been categorized as class II mixed-valence according to the classification proposed by Robin and Day. Of importance is the observation that these two compounds are more active against human A549 and H1975 non-small-cell lung cancer cells than their congeners, which do not show MV characteristics. Moreover, the anticancer activity of MV species competes or surpasses, dependent on the cell line, the activity of reference anticancer drugs such as cisplatin, tamoxifen, and 5-fluorouracil. The most active from the entire series of compounds was the binuclear thymidine derivative with the lowest IC50 value of 5 ± 2 µM against lung H1975 cancer cells. The major mechanism of antiproliferative activity for the investigated MV compounds is based on reactive oxygen species generation in cancer cells. This hypothesis was substantiated by EPR spin-trapping experiments and the observation of decreased anticancer activity in the presence of N-acetyl cysteine (NAC) free-radical scavenger.
Asunto(s)
Antineoplásicos , Carcinoma de Pulmón de Células no Pequeñas , Neoplasias Pulmonares , Antineoplásicos/química , Electrónica , Humanos , Metalocenos , Especies Reactivas de Oxígeno/metabolismo , Triazoles/químicaRESUMEN
Open-shell non-alternant polycyclic hydrocarbons (PHs) are attracting increasing attention due to their promising applications in organic spintronics and quantum computing. Herein we report the synthesis of three cyclohepta[def]fluorene-based diradicaloids (1-3), by fusion of benzo rings on its periphery for the thermodynamic stabilization, as evidenced by multiple characterization techniques. Remarkably, all of them display a very narrow optical energy gap (Eg opt =0.52-0.69â eV) and persistent stability under ambient conditions (t1/2 =11.7-33.3â h). More importantly, this new type of diradicaloids possess a low-lying triplet state with an extremely small singlet-triplet energy gap, as low as 0.002â kcal mol-1 , with a clear dependence on the molecular size. This family of compounds thus offers a new route to create non-alternant open-shell PHs with high-spin ground states, and opens up novel possibilities and insights into understanding the structure-property relationships.
RESUMEN
Lanthanide dimetallofullerenes with single-electron M-M bonds are an important class of single molecular magnets and qubit candidates, but stabilization of their unique electronic and spin structure in the form of a neutral molecule requires functionalization of the fullerene cage with a single radical group. The lack of selectivity of the currently available procedure results in a complicated and tedious separation process. Here we demonstrate that electrophilic trifluoromethylation of a mixture of metallofullerene anions with Umemoto reagent II is highly selective toward M2@C80- (M = Tb, Y) anions, yielding M2@C80(CF3) monoadducts as the main reaction product. Single-crystal X-ray diffraction study proved attachment of the CF3 group to the pentagon/hexagon/hexagon junction and revealed that positions of metal atoms inside the fullerene cage in the cocrystal with NiOEP are strongly related to the position of the porphyrin moieties. Magnetic characterization of Tb2@C80(CF3) showed that it is a robust single-molecule magnet with broad magnetic hysteresis, 100 s blocking temperature of 25 K, and the relaxation barrier of 801(4) K, corresponding to the flipping of the Tb magnetic moment in the strongly ferromagnetically coupled [Tb3+-e-Tb3+] spin system.