Porphyrin Dimers and Arrays

Abstract

Current applications of porphyrins in medicine and optics, such as photodynamic therapy or nonlinear absorbers, increasingly require the use of far-red absorbing dyes. Modifications of the porphyrin structure to accommodate these conditions can be achieved by extending the conjugation of the porphyrin π-system, which causes a bathochromic shift in the absorption spectrum. Thus, conjugated porphyrin oligomers have found widespread use. However, past synthetic strategies have mainly targeted symmetric porphyrin dimers, trimers, and oligomers, which limit the practical use of such chromophores. Here, a series of symmetric and unsymmetric dimeric and trimeric porphyrin systems, which are connected by conjugated linkers, namely alkyne and phenylacetylene, were synthesized by palladium-catalyzed C-C coupling re-

Amplified Two‐Photon Absorption in Trans‐A2B2‐Porphyrins Bearing Nitrophenylethynyl Substituents

“…Meso -substituted arylethynyl porphyrins ever since the first seminal contributions by Therien [10] and others [11] continue to attract attention. [12] The ethynyl moieties elongate the π-conjugation pathway, causing a characteristic bathochromatically shifted absorption. [13, 14] Because simple tetraarylporphyrins lack any considerable 2PA enhacement, [3] it would be of most interest to study the effect of various end groups.…”

Synthetic, Structural, and Spectroscopic Studies of Bis(porphyrinzinc) Complexes Linked by Two‐Atom Conjugating Bridges

“…[14] A similar attempt with 7 (Scheme 2) led only to a mixture of deformylated 6 and alcohol 8 with traces of meso-methylNiTriPP, which was identified by comparison with a sample prepared by our exhaustive reduction method in DMF/water under microwave irradiation. [21] Both the Ni II complexes (10)(11)(12) and the free bases (13 and 14) were tried, but neither 9 nor its free-base analog 15 were identified in the crude products. [21] Both the Ni II complexes (10)(11)(12) and the free bases (13 and 14) were tried, but neither 9 nor its free-base analog 15 were identified in the crude products.…”

“…When we began this work, the ethane, Scheme 1. ethyne, and imine diporphyrins 1, 3, and 4 had not been previously reported, although analogs with different peripheral substitution were known for 3 [7,9,11] and 4. [12] Our group published the first reports of the syntheses of 2 [4] and 5. [12] Our group published the first reports of the syntheses of 2 [4] and 5.…”

Studying the intersystem crossing rate and triplet quantum yield of meso-substituted porphyrins by means of pulse train fluorescence technique

“…in photodynamic therapy [34]. For spectroscopic studies, the corresponding porphyrins were dissolved in dimethyl sulfoxide (DMSO) which was chosen for its low volatility and high solubility of the porphyrins studied therein.…”