Ground state singlet-to-triplet conversion of copper corrole radical byβ-benzo-fusion

Materials with facilely tunable spin configurations based on metal-radical coordination systems have potential applications for electronics and spintronics.Here,we report the ground state conversion of copper corrole radicals from singlet to triplet via the extension of theπ-conjugation system by benzo-fusion at theβ-position of corrole ligand.NMR spectroscopy,SQUID measurements and computational studies all support the ferromagnetic coupling between the Cu(II)center and corroleπ-radical of benzo-fused copper corrole 2-Cu,which is in sharp contrast with the antiferromagnetic coupling in regular non-extended copper corroles.The triplet 2-Cu is highly stable in air,and X-ray diffraction analysis revealed its unique highly planar corrole macrocycle.This work offers a promising strategy for creating high-spin systems in non-innocent metallocorroles.

Near-infrared absorbing(>700 nm)aza-BODIPYs by freezing the rotation of the aryl groups

The typical aza-BODIPYs in the dye family are known for bright fluorescence,excellent stability,and tunable absorption wavelengths.Hence,these dyes are attracting the increasing attention.Aza-BODIPYs having the maxima absorption in the near-infrared(NIR)region(650-900 nm)are very favorable for bioimaging in vivo due to the less photo-damage,deeper tissue penetration,and less interference from background auto-fluorescence by biomolecules in the living systems.Many strategies have been employed to modify the structures of the aza-BODIPY core to provide the NIR absorbing dyes.Among these,the most effective method is the fusion of the aromatic rings in aza-BODIPY system.This review allsidedly summarizes the recent development of ring-fused aza-BODIPY dyes(λ_(abs)>700 nm)focusing on the design,synthesis,and potential applications in the NIR region since 2002.