Neutral {CpFe II (CO) 2 [Sn II (Pc •3– )]} {Cp is cyclopentadienyl ( 1 , 2 ) or Cp* is pentamethylcyclopentadienyl ( 3 ); Pc: phthalocyanine}, {Cp*Fe II (CO) 2 [Sn II (Nc •3– )]} ( 4 , Nc: naphthalocyanine), and {CpFe II (CO) 2 [Sn II (TPP •3– )]} ( 5 , TPP: tetraphenylporphyrin) complexes in which CpFe II (CO) 2 fragments (Cp: Cp or Cp*) are coordinated to Sn II (macrocycle •3– ) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFe I (CO) 2 (Cp: Cp or Cp*) to [Sn II (macrocycle 2− )] to form the diamagnetic Fe II and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C–N imine or C–C meso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFe II (CO) 2 Sn II (macrocycle •3– )} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π–π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J / k B = −78 and −85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer ( J intra ) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors ( J inter ). Compound 2 demonstrates large intradimer interaction of J intra / k B = −54 K and essentially weaker interdimer exchange interactions of J ...
Coordination of tin(II) phthalocyanine to transition metal carbonyl clusters in neutral {Sn(II){Pc(2-)}}(0) or radical anion {Sn(II){Pc(•3-)}}(-) states is reported. Direct interaction of Co4(CO)12 with {Sn(II){Pc(2-)}}(0) yields crystalline complex {Co4(CO)11·Sn(II){Pc(2-))} (1)....
BackgroundThe steady rise in the spread of multidrug-resistant tuberculosis (MDR-TB) and extensively drug-resistant tuberculosis (XDR-TB) requires rapid and reliable methods to identify resistant strains. The current molecular methods to detect MTB resistance to second-line drugs either do not cover an extended spectrum of mutations to be identified or are not easily implemented in clinical laboratories. A rapid molecular technique for the detection of resistance to second-line drugs in M. tuberculosis has been developed using hybridisation analysis on microarrays.MethodsThe method allows the identification of mutations within the gyrA and gyrB genes responsible for fluoroquinolones resistance and mutations within the rrs gene and the eis promoter region associated with the resistance to injectable aminoglycosides and a cyclic peptide, capreomycin. The method was tested on 65 M. tuberculosis clinical isolates with different resistance spectra that were characterised by their resistance to ofloxacin, levofloxacin, moxifloxacin, kanamycin and capreomycin. Also, a total of 61 clinical specimens of various origin (e.g., sputum, bronchioalveolar lavage) were tested.ResultsThe sensitivity and specificity of the method in the detection of resistance to fluoroquinolones were 98% and 100%, respectively, 97% and 94% for kanamycin, and 100% and 94% for capreomycin. The analytical sensitivity of the method was approximately 300 genome copies per assay. The diagnostic sensitivity of the assay ranging from 67% to 100%, depending on the smear grade, and the method is preferable for analysis of smear-positive specimens.ConclusionsThe combined use of the developed microarray test and the previously described microarray-based test for the detection of rifampin and isoniazid resistance allows the simultaneous identification of the causative agents of MDR and XDR and the detection of their resistance profiles in a single day.
Reduction of copper(II) octafluoro- {CuII(F8Pc)} and hexadecafluorophthalocyanines {CuII(F16Pc)} by NaCpCo(CO)2 in the presence of cryptand[2.2.2] yields new crystalline {cryptand(Na+)}[CuII(F8Pc)•3-]- 2C6H4Cl2(1) and {cryptand(Na+)}2[CuII(F16Pc)4-]2- C6H14 (2) salts. Together with two previously characterized...
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