Dinaphthoporphycene
(DNP) has emerged as a versatile ligand undergoing
large out-of-plane distortion to form a cis-bimetallic complex with
Pd(II) using Pd(OAc)2 and out-of-plane monometallic complexes
with Pd(acac)2 and PtCl2(PhCN)2.
Herein, we are finally able to synthesize the in-core complex with
Pd(II) using PdCl2(PhCN)2 or PdCl2. The crystal structure shows the palladium ion resides slightly
above the N4-core, with the Pd(II) dimensionally dissenting with the
typical square planarity displayed by the reported in-core DNP complexes
with Ni(II) and Cu(II) ions. The deformed complex displays a blue
shift in the absorption spectra compared to DNP and its metallo-derivatives.
PdDNP exhibits a moderate singlet oxygen generation ability (18%).
Two symmetry reduction induced unsymmetrical porphyrins (2.0.2.0) were synthesized and characterized with distinct structural, optoelectronic and nonlinear optical properties.
We
have designed and synthesized 3,6,13,16-tetrapropylporphycene
for the first time as its alkyl analogue from ethyl 4-propyl-1H-pyrrole-2-carboxylate. The substituent effect was found
to be more intense than reported positional isomeric tetrapropylporphycenes.
The freebase porphycene exhibited moderate fluorescence and complexation
ability with divalent metal ions, including Zn(II), which displayed
an enhanced emission quantum yield (∼30%). The Pd(II) complex
and freebase β-tetrabromoporphycene generated singlet oxygen
efficiently (75 and 51%, respectively) and, hence, may find application
as potential photosensitizers in photodynamic therapy.
A novel A2B-type B(III)subchlorin has been synthesized for the first time in two ways possessing two different ester moieties upon macrocyclic periphery from meso-diethoxycarbonyl tripyrrane. Its photophysical and electrochemical properties have been explored. Introduction of the third meso-substituent resulted in the synthesis of the B(III)subchlorin as the major product with the formation of minor oxidized B(III)subporphyrin analogue. This subchlorin derivative was found to generate singlet oxygen much efficiently with quantum yield ([Formula: see text] 0.88.
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