Heteroleptic FeII Complexes of 2,2′‐Biimidazole and Its Alkylated Derivatives: Spin‐Crossover and Photomagnetic Behavior

Three iron(II) complexes, [Fe(TPMA)(BIM)](ClO₄)₂?0.5H₂O ( 1 ), [Fe(TPMA)(XBIM)](ClO₄)₂ ( 2 ), and [Fe(TPMA)(XBBIM)](ClO₄)₂ ?0.75CH₃OH ( 3 ), were prepared by reactions of Fe^II perchlorate and the corresponding ligands (TPMA=tris(2‐pyridylmethyl)amine, BIM=2,2′‐biimidazole, XBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐biimidazole, XBBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐bibenzimidazole). The compounds were investigated by a combination of X‐ray crystallography, magnetic and photomagnetic measurements, and Mössbauer and optical absorption spectroscopy. Complex 1 exhibits a gradual spin crossover (SCO) with T_1/2=190 K, whereas 2 exhibits an abrupt SCO with approximately 7 K thermal hysteresis (T_1/2=196 K on cooling and 203 K on heating). Complex 3 is in the high‐spin state in the 2–300 K range. The difference in the magnetic behavior was traced to differences between the inter‐ and intramolecular interactions in 1 and 2 . The crystal packing of 2 features a hierarchy of intermolecular interactions that result in increased cooperativity and abruptness of the spin transition. In 3 , steric repulsion between H atoms of one of the pyridyl substituents of TPMA and one of the benzene rings of XBBIM results in a strong distortion of the Fe^II coordination environment, which stabilizes the high‐spin state of the complex. Both 1 and 2 exhibit a photoinduced low‐spin to high‐spin transition (LIESST effect) at 5 K. The difference in the character of intermolecular interactions of 1 and 2 also manifests in the kinetics of the decay of the photoinduced high‐spin state. For 1 , the decay rate constant follows the single‐exponential law, whereas for 2 it is a stretched exponential, reflecting the hierarchical nature of intermolecular contacts. The structural parameters of the photoinduced high‐spin state at 50 K are similar to those determined for the high‐spin state at 295 K. This study shows that N‐alkylation of BIM has a negligible effect on the ligand field strength. Therefore, the combination of TPMA and BIM offers a promising ligand platform for the design of functionalized SCO complexes.     

Directional change of magnetic easy axis of arrays of cobalt nanowires: Role of non-dipolar magnetostatic interaction

Room temperature magnetization of two dimensional (2D) arrays of cobalt nanowires (NWs) having diameter 50 and 150 nm prepared by electrodeposition are studied in details. Diffraction patterns of the NWs reveal that the crystallites of the NWs become more textured on decreasing their diameter. Magnetic hysteresis loop measurements show the magnetic easy axis changes its direction from axial to perpendicular direction of NWs on increasing the length of the NWs. The magnetostatic interaction among the NWs, known as the key factor in defining the easy direction is found not to be dipolar at all the circumstances. An aspect ratio (length/diameter of NWs) dependence of the non-dipolar interaction in 150 nm NWs is evident from the static magnetization as well as from ferromagnetic resonance (FMR) measurements.     

Stereoselective Synthesis of Diaminosuberic Acid Via a Chiral Alkynyl Oxazolidine

A novel, stereoselective synthesis of enantiomerically pure, N-protected diaminosuberic acid (6) is presented. The key step in the synthesis is the oxidative dimerization of the chiral alkynyl oxazolidine (2).     

A total synthesis of 11-O-methyldebenzoyltashironin

A concise total synthesis of 11-O-methyldebenzoyltashironin is reported in which oxidative dearomatization-IMDA-RCM triad constitutes the key ring forming steps, while an unorthodox DIBAL-H mediated stereo- and regioselective reductive epoxide openings and implementation of the vinyl bromide-carbonyl equivalency concept were pivotal to the success of this endeavor.     

Vertically aligned N-doped carbon nanotubes by spray pyrolysis of turpentine oil and pyridine derivative with dissolved ferrocene

Vertically aligned nitrogen-doped carbon nanotubes were synthesized from the pyrolysis of a mixture of turpentine oil, 4-tert-butylpyridine (C₉H₁₃N) and ferrocene on silicon and quartz substrate in nitrogen atmosphere at 700 °C by simple spray pyrolysis technique. SEM, TEM, TGA/DTA, Raman spectroscopy, XPS and electron probe micro analysis (EPMA) techniques were used to characterize the structural analysis and composition of the as-grown N-doped carbon nanotubes. Morphology of the films was greatly affected by the nature of the substrate. From the XPS and EPMA data, it was found that nitrogen content of the nanotubes were 1.6 at.% and 2 at.% on silicon and quartz substrate, respectively. Our studies show that two different types of N atoms can be present in these materials. These are ‘pyridinic’ and ‘graphitic’ nitrogen with binding energies of 398.2 eV and 400.4 eV, respectively. Raman spectroscopy reveals that graphitization of carbon nanotubes grown on silicon is better than nanotubes grown on quartz substrate. Thermogravimetric analysis showed that the thermal stability of as-prepared nanotubes grown on silicon substrate is higher than the nanotubes deposited on quartz substrate.     

Reversible fluorescence sensing of Zn2+ based on pyridine-constrained bis(triazole-linked hydroxyquinoline) sensor

Zinc ion (Zn²⁺) is an important and a most useful biological trace nutrient responsible for the activity of several enzymes. Zn²⁺ concentrations in the environment as well as in the human body increase beyond permissible limits as a consequence of its mining and widespread industrial applications. Such excess Zn²⁺ concentrations are toxic to humans and many aquatic organisms. The magnetic inertness and spin paired electronic configuration of Zn²⁺ makes it hard to detect by common analytical techniques. Therefore, fluorometric detection using chemosensor is the most effective tool for the environmental and biological detection of Zn²⁺. We have developed a novel pyridine-constrained bis(triazole-linked hydroxyquinoline) ligand as a reversible fluorescent chemosensor for Zn²⁺. The symmetrical ligand is highly selective for Zn²⁺ and fluoresces brightly upon complexation compared with other metal ions based on chelation-enhanced fluorescence mechanism. Interestingly, free ligand can be regenerated by treating the ligand–Zn²⁺ complex with aqueous ammonia.     

Photoinduced DNA Cleavage Reactions by Designed Analogues of Co(III)-Bleomycin: The Metalated Core Is the Primary Determinant of Sequence Specificity

A 2,4'-bithiazole group has been covalently attached to the Co(III) complex of a designed ligand PMAH that mimics the metal-binding locus of the antitumor drug bleomycin (BLM). The deprotonated PMA(-) ligand binds Co(III) via five nitrogens located in primary and secondary amines, a pyrimidine and an imidazole ring, and a peptide moiety. The 2,4'-bithiazole group is tethered to the [Co(PMA)](2+) unit via an imidazole that is connected to the bithiazole moiety with a (CH(2))(3) spacer. The structure of this hybrid analogue, namely, [Co(PMA)(Bit)]Cl(2) (7, Bit = 2'-methyl-2,4'-bithiazole-4-carboxamido-N'-(3-propyl)imidazole) has been established by spectroscopic techniques. 7 promotes photocleavage of DNA at micromolar concentrations. Unlike simpler analogues like [Co(PMA)(H(2)O)](2+) and [Co(PMA)Cl)](+) which induce random DNA cleavage upon UV illumination, 7 exhibits sequence specificity in the DNA photocleavage reaction. Intriguing is to note that 7 exhibits the same 5'GG-N3' sequence preference as another hybrid analogue [Co(PMA)(Int-A)]Cl(2) (6, Int-A = acridine-9-carboxamido-N'-(3-propyl)imidazole) that contains an acridine moiety as the DNA-binding group. The observed sequence specificity of 6 and 7 therefore does not reflect the sequence preferences of the DNA-binding groups (acridine and bithiazole). The results indicate that the metalated core of the hybrid analogues, i.e., the [Co(PMA)](2+) unit is the key factor in determining their sequence specificity.