Synthesis, spectroscopic and theoretical investigations of hitherto unknown highly stable nickel, and copper organometallic complexes of trans-doubly N-confused porphodimethenes are reported. The distorted square planar Ni organometallic complex has been susceptible to trivial +2 oxidation state of Ni via single CH activation and another weak Ni-C bond with C-H agostic interaction while the diamagnetic near square planar copper complex exhibits the atypical +3 oxidation state of copper via double inner CH activation. The conformational preorganization and metallation induced conformational reorganization owing to the formation of M-C bond formations by both nickel and copper have been thoroughly investigated by various spectroscopic techniques and in-depth DFT level theoretical calculations.
Judicious syntheses, spectroscopic
analyses, and solid state structural
evidence of two structural variants (with planar geometry) of strongly
aromatic hybrid [30] E-ethylene bridged hexaphyrins
(2.1.1.2.1.1) exhibiting strong NIR absorption are reported. The induced
correspondence of fused phenanthrene on the pyrrole moieties has led
to a further red-shift of up to ∼45 nm in the neutral and protonated
form of the macrocycles. The electronic nature and aromaticity of
both hexaphyrins are fully supported by DFT calculations.
Synthesis, spectroscopic and solid state structural proof of hitherto unknown highly stable meso-pyrrole appended expanded dioxaphlorin is reported. The macrocycle was susceptible to NH deprotonation upon TBAF titration leading to NIR absorption with vivid colour change to the naked eye paving the way towards the application as a fluoride ion sensor. Contrarily, efficient conversion to aromatic dioxasapphyrin has been anticipated upon trifluoroacetic acid reaction owing to facile elimination of meso-appended pyrrole ring. The conformational preorganzation and anion induced conformational reorganization owing to the base promoted NH deprotonation are thoroughly investigated by various spectroscopic techniques and DFT level theoretical calculations.
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