Laser induced protonation of free base porphyrin in chloroform results in the enhancement of positive nonlinear absorption due to conformational distortion

Zawadzka, Monika; Wang, Jun; Blau, Werner J.; Senge, Ma­thias O.

doi:10.1142/s108842461350082x

Cited by 15 publications

(7 citation statements)

References 22 publications

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“…[101] Herein, the cationic porphyrin architectures showed asignificantly higher catalytic activity than aggregates under neutral conditions.P orphyrin dications have also generated some interest, for example,innonlinear optics (NLO), where laserinduced protonation of free-base porphyrin in chloroform gave apositive nonlinear absorption (NLA) due to conformational distortion. [102] Often, the more elusive porphyrin monocations are also saddle-distorted, although tendentially less than the corresponding diacids [103] and stand as a" missing species" in porphyrin chemistry since they are generally difficult to produce,c haracterize,a nd isolate.P orphyrin monoacids are usually less stable than their diprotonated counterparts;i tis likely that al arge saddle-distortion destabilizes the monoacids because their out-of-plane distortion significantly reduces the steric crowding of the remaining unprotonated nitrogen atom. This leads to the uptake of as econd proton being more energetically favorable than the first.…”

Section: Porphyrin (Di)cationsmentioning

confidence: 99%

“…Herein, the cationic porphyrin architectures showed a significantly higher catalytic activity than aggregates under neutral conditions. Porphyrin dications have also generated some interest, for example, in nonlinear optics (NLO), where laser‐induced protonation of free‐base porphyrin in chloroform gave a positive nonlinear absorption (NLA) due to conformational distortion …”

Section: Accessing N−h Units In Porphyrinsmentioning

confidence: 99%

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Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

Kielmann

Senge

2018

Angew Chem Int Ed

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The core N-H units of planar porphyrins are often inaccessible to forming hydrogen-bonding complexes with acceptor molecules. This is due to the fact that the amine moieties are "shielded" by the macrocyclic system, impeding the formation of intermolecular H-bonds. However, methods exist to modulate the tetrapyrrole conformations and to reshape the vector of N-H orientation outwards, thus increasing their availability and reactivity. Strategies include the use of porpho(di)methenes and phlorins (calixphyrins), as well as saddle-distorted porphyrins. The former form cavities due to interruption of the aromatic system. The latter are highly basic systems and capable of binding anions and neutral molecules via N-H⋅⋅⋅X-type H-bonds. This Review discusses the role of porphyrin(oid) ligands in various coordination-type complexes, means to access the core for hydrogen bonding, the concept of conformational control, and emerging applications, such as organocatalysis and sensors.

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Section: Porphyrin (Di)cationsmentioning

confidence: 99%

Section: Accessing N−h Units In Porphyrinsmentioning

confidence: 99%

Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

Kielmann

Senge

2018

Angew Chem Int Ed

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“…A mechanism of counter‐ion coordination which involves a protonation of a porphyrin ring is of a great importance [37] . The ionized tetrapyrrole compounds have a huge potential in nonlinear optics [38] . The protonation of free‐base porphyrins and their structural analogues is among the fundamental and most important reactions.…”

Section: Introductionmentioning

confidence: 99%

Coordination Properties of Porphyrin Analogues Ionized Forms by Experiment and Quantum Chemistry: 5,10,15,20‐Tetraphenyl‐21‐thia‐ and 5,10,15,20‐Tetraphenyl‐21,23‐Dithiaporphyrins

et al. 2022

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Modification of porphyrins by a replacement of N atom(s) with a heteroatom(s) resulted in the so called heteroporphyrins which exhibit interesting physicochemical properties. In this work, the spectral properties of ions and neutral forms of 5,10,15,20-tetraphenyl-21,23-dithia porphyrin (S 2 PP) and 5,10,15,20-tetraphenyl-21-thia-porphyrin (HSPP) have been investigated. According to the spectrophotometric analysis in acetonitrile -perchloric acid solution, the dication H 2 S 2 PP 2 + reveals an ability to coordinate two ClO 4 À anions, which was not found for H 3 SPP 2 + . This fact, as observed in the UV-Vis absorption spectra, indicates the possibility of exhibiting chemosensory properties of S 2 PP molecules. The geometries of the neutral and ionized forms were derived from B3LYP/cc-pVTZ calculations. The perimeters of the cavities increase in the series: H 2 PP!HSPP!S 2 PP. This trend is kept in case of the ionized forms; the protonation expands the cavity perimeter. Electron density distributions were analyzed in terms of quantum theory of atoms in molecules (QTAIM). The UV-vis spectra simulated on the base of the TD-DFT calculations match the experimental results.

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“…Meanwhile, due to the structural adjustability, unique electronic and photophysical properties of porphyrins, porphyrins have broad application in various areas and good prospects ( Zhang et al, 2018 ; Chen et al, 2020 ; Asghar et al, 2021 ; Liu and Cheng, 2021 ). Particularly, the NLO performance of porphyrins could be improved by the flexible modification of peripheral substituents or the hybridization with other materials ( Zawadzka et al, 2013 ; Woller et al, 2016 ; Hu et al, 2018 ; Biswal et al, 2019 ; Samal et al, 2019 ; Liu J. L. et al, 2020 ; Liu Z. et al, 2020 ; Liu and Cheng, 2021 ; Ramasamy et al, 2022 ). However, previous research indicated the self-aggregate behavior of porphyrins could lead to the formation of large macro-scale and fractal structures, causing a negative impact in the development of NLO devices in practice ( Kalachyova et al, 2014 ).…”

Section: Introductionmentioning

confidence: 99%

Enhanced non-linear optical properties of porphyrin-based polymers covalently functionalized with graphite phase carbon nitride

et al. 2022

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In our work, a flurry of original porphyrin-based polymers covalently functionalized g-C3N4 nanohybrids were constructed and nominated as PPorx-g-C3N4 (x = 1, 2 and 3) through click chemistry between porphyrin-based polymers with alkyne end-groups [(PPorx-C≡CH (x = 1, 2 and 3)] and azide-functionalized graphitic carbon nitride (g-C3N4-N3). Due to the photoinduced electron transfer (PET) between porphyrin-based polymers [PPorx (x = 1, 2 and 3)] group and graphite phase carbon nitride (g-C3N4) group in PPorx-g-C3N4 nanohybrids, the PPorx-g-C3N4 nanohybrids exhibited better non-linear optical (NLO) performance than the corresponding PPorx-C≡CH and g-C3N4-N3. It found that the imaginary third-order susceptibility (Im [χ(3)]) value of the nanohybrids with different molecular weight (MW) of the pPorx group in the nanohybrids ranged from 2.5×103 to 7.0 × 103 g mol−1 was disparate. Quite interestingly, the Im [χ(3)] value of the nanohybrid with a pPorx group’s MW of 4.2 × 103 g mol−1 (PPor2-g-C3N4) was 1.47 × 10–10 esu, which exhibited the best NLO performance in methyl methacrylate (MMA) of all nanohybrids. The PPorx-g-C3N4 was dispersed in polymethyl methacrylate (PMMA) to prepare the composites PPorx-g-C3N4/PMMA since PMMA was widely used as an alternative to glass. PPor2-g-C3N4/PMMA showed the excellent NLO performance of all nanohybrids with the Im [χ(3)] value of 2.36 × 10–10 esu, limiting threshold of 1.71 J/cm2, minimum transmittance of 8% and dynamic range of 1.09 in PMMA, respectively. It suggested that PPorx-g-C3N4 nanohybrids were potential outstanding NLO materials.

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Laser induced protonation of free base porphyrin in chloroform results in the enhancement of positive nonlinear absorption due to conformational distortion

Cited by 15 publications

References 22 publications

Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles

Coordination Properties of Porphyrin Analogues Ionized Forms by Experiment and Quantum Chemistry: 5,10,15,20‐Tetraphenyl‐21‐thia‐ and 5,10,15,20‐Tetraphenyl‐21,23‐Dithiaporphyrins

Enhanced non-linear optical properties of porphyrin-based polymers covalently functionalized with graphite phase carbon nitride

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