5,15‐A2B2‐ and 5,15‐A2BC‐Type Porphyrins with Donor and Acceptor Groups for Use in Nonlinear Optics and Photodynamic Therapy

Senge, Ma­thias O.; Fazekas, Marijana; Pintea, Monica; Zawadzka, Monika; Blau, Werner J.

doi:10.1002/ejoc.201100641

Cited by 120 publications

(24 citation statements)

References 59 publications

(16 reference statements)

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“…Some, like 5,15-diphenylporphyrin 11, are commercially available and/or can be prepared on a large scale [ 26 , 27 ]. They typically serve as starting materials for post-cyclization modification of porphyrins [ 28 , 29 , 30 , 31 , 32 , 33 , 34 ] but have also found applications in their own right, e.g., as photosensitizers in photodynamic therapy [ 35 ].…”

Section: Introductionmentioning

confidence: 99%

Weak Interactions and Conformational Changes in Core-Protonated A2- and Ax-Type Porphyrin Dications

et al. 2020

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Individual chemical motifs are known to introduce structural distortions to the porphyrin macrocycle, be it in the core or at the periphery of the macrocycle. The interplay when introducing two or more of these known structural motifs has been scarcely explored and is not necessarily simply additive; these structural distortions have a chance to compound or negate to introduce new structural types. To this end, a series of compounds with complementary peripheral (5,15-disubstitution) and core (acidification) substitution patterns were investigated. The single-crystal X-ray structures of 18 5,15-diphenylporphyrin, 5,15-diphenylporphyrindi-ium diacid, and related compounds are reported, including the first example of a 5,15-dialkylporphyrindi-ium. Normal-coordinate structural decomposition (NSD) analysis is used for a detailed analysis of the conformation of the porphyrin subunit within the crystal structures. An elongation of porphyrin macrocycles along the C5,C15- axis (B2g symmetry) is observed in all of the free base porphyrins and porphyrin dications; distance across the core is around 0.3 Å in the free base and diacid compounds, and more than doubled in 5,15-dipentylporphyrin and 5,15-dipentylporphyrindi-ium diacid. While the free base porphyrins are largely planar, a large out-of-plane distortion can be observed in 5,15-diphenylporphyrin diacids, with the expected “projective saddle” shape characteristic for such systems. The combination of these two distortions (B2u and B2g) from regular porphyrin structure results in a macrocycle best characterized in the chiral point-group D2. A rare structural type of a cis-hydrogen bond chelate is observed for 5,15-dipentylporphyrindi-ium diacid, which adopts an achiral C2v symmetry. Crystallographic data indicate that the protonated porphyrin core forms hydrogen bonding chelates (N-H⋯X⋯H-N) to counter-anions. Weaker interactions, such as induced intramolecular C-H⋯O interactions from the porphyrin periphery are described, with distances characteristic of charge-assisted interactions. This paper offers a conceptual framework for accessing porphyrin macrocycles with designable distortion and symmetry, useful for the selective perturbation of electronic states and a design-for-application approach to solid state porphyrin materials.

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Section: Introductionmentioning

confidence: 99%

Weak Interactions and Conformational Changes in Core-Protonated A2- and Ax-Type Porphyrin Dications

et al. 2020

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“…We noted a similar trend for structurally diverse porphyrins of the 5,15-A 2 B 2 , 5,15-A 2 BC series before. 14,36 The same observation can be applied to the 5,10-A 2 B 2 compounds studied, i.e., both κ 1 and κ 2 increase with the maximum of the Soret band. …”

Section: Photochemical and Photobiological Sciences Papermentioning

confidence: 61%

Nonlinear absorption properties of 5,10-A2B2porphyrins—correlation of molecular structure with the nonlinear responses

Zawadzka

Wang

Blau

et al. 2013

Photochem Photobiol Sci

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The nonlinear absorption properties of two series of novel free base and metalated meso 5,10-A 2 B 2 substituted porphyrins, both bearing p-tolyl as an A substituent and TMS-ethynyl or bromine as a B substituent, were investigated with the open Z-scan technique at 532 nm in the ns time regime. Most of the compounds exhibited a transmission drop with increasing input fluence. This behavior is desirable for their applications in optical limiting. More complex responses: a drop in transmission followed by an increase in transmission or an increase in transmission followed by a transmission drop, with increasing input fluence, were detected for certain compounds. All of the recorded responses were successfully fitted with a four-level model with simultaneous two-photon absorption arising from the higher excited states (consecutive one-+ one-+ two-photon absorption). The TMS-ethynyl group was found to be a more efficient meso substituent in optical limiting than the bromine atom. Indium, lead and zinc complexes with TMS-ethynyl substituents were the strongest positive nonlinear absorbers amongst compounds studied which makes them the most interesting candidates for optical limiting application.

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“…58 The functionalization of A 2 -type porphyrins as starting materials by organolithium and palladium catalyzed cross-coupling reactions is an efficient means to enable the introduction of almost any desired meso substituent. 59 A convenient preparation of analytically pure multigram batches of 5-substituted dipyrromethanes has been achieved by the acid-catalyzed condensation of an aldehyde with excess pyrrole in solvent-free conditions. 60 Condensation of a dipyrromethane with an aldehyde in a MacDonald-type "2 + 2" condensation, 61 has been used to prepare a wide range of meso-substituted transporphyrins.…”

Section: A Synthetic Approachesmentioning

confidence: 99%

Strategic Synthetic Approaches to Porphyrin-Based Artificial Light-Harvesting Systems for Solar Energy Utilization

Coutsolelos¹,

Ladomenou²,

Charalambidis³

et al. 2014

Handbook of Porphyrin Science

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5,15‐A₂B₂‐ and 5,15‐A₂BC‐Type Porphyrins with Donor and Acceptor Groups for Use in Nonlinear Optics and Photodynamic Therapy

Cited by 120 publications

References 59 publications

Weak Interactions and Conformational Changes in Core-Protonated A2- and Ax-Type Porphyrin Dications

Weak Interactions and Conformational Changes in Core-Protonated A2- and Ax-Type Porphyrin Dications

Nonlinear absorption properties of 5,10-A2B2porphyrins—correlation of molecular structure with the nonlinear responses

Strategic Synthetic Approaches to Porphyrin-Based Artificial Light-Harvesting Systems for Solar Energy Utilization

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