Ultrafast and short pulse optical nonlinearities of meso-tetrakis-(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl) porphyrin and its metal complexes

Materials with large and quick non-linear optical response, excellent photo thermal stability, cost effectiveness and off resonant non-linear absorption (NLA) are essential requirements for a good optical limiting (OL). Among them, organic systems and π-conjugated polymers are getting special interest because of their flexibility in structural modification that leads to the tuning of optical and electronic properties that are suitable for working under large bandwidth. Here, we report a drastic enhancement of non-linear optical activity and exceptional OL action of two organic-inorganic hybrid system based on BODIPY and Au and Ag nanoparticles (NPs). The organic system taken was certain set of BODIPYs with different substitution at the para and meta positions. All the compounds were found to be exhibiting good reverse saturable absorption (RSA) behaviour and negative non-linear refraction property. An attempt was made to improve the non-linear optical (NLO) property of the BODIPY by forming nanohybrids with Au and Ag NPs, and the best NLO active candidate among the studied system was chosen for it. A significant enhancement in NLO property was observed on hybrid system formation. The optical limiting (OL) threshold of the hybrid (1 J/cm 2) was reduced almost 1/5 times than that of the parent compound (5.2 J/cm 2), and this value is comparable with the benchmark OL materials like C 60. The mechanism behind the NLA is found to be the combination of excited state absorption (ESA) and twophoton absorption (TPA). The enhanced NLA and OL action of C Ag/Au nanohybrids are attributed to the synergetic effect among the two parent components as well as the local field effects of NPs. Enhancement in non-linear optical property is found to be stronger in hybrid system with Au NPs and is due to the resonant charge transfer and intense local field effect on exciting with 532-nm pulse compared with that of Ag NPs. Both the parent compounds and the nanohybrids exhibit negative non-linearity, and the non-linear

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“…As the beam propagates through the medium, it acquires an additional phase shift because of induced lensing effect. [ 53,54 ]…”

Section: Resultsmentioning

confidence: 99%

“…As the beam propagates through the medium, it acquires an additional phase shift because of induced lensing effect. [53,54] Figure 12b shows the CBO Z scan signatures hybrid system, and its constituents. As discussed above here also, all the compounds exhibit negative non-linearity.…”

Section: Non-linear Refraction Studiesmentioning

confidence: 99%

An insight into phenomenal optical non‐linearities arising from synergistic relationship between selected BODIPYs and noble metal nanoparticles

Edappadikkunnummal

Prasannan

Francis

et al. 2020

Applied Organom Chemis

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“…Possible application of the fluorinated porphyrin materials in the field of non-linear optics has been studied as well. 124,125 Synthons involving nitro-functional groups A different class of weak intermolecular interactions that are manifested in various supramolecular systems involves the nitro group. 126,127 The -NO 2 function can serve as an acceptor for C-H⋯O hydrogen bonds, take part in N⋯O stacking interactions (that can involve two or more nitro functions) as well as in the attractive O⋯π motif between NO 2 and an adjacent π-system.…”

Section: Interaction Synthons Involving Fluorine Atomsmentioning

confidence: 99%

Porphyrin-based assemblies directed by non-covalent interactions: highlights of recent investigations

2016

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This paper addresses a series of recent investigations into crystalline porphyrin-based assemblies directed by non-covalent and non-coordinative interactions. It describes attractive design strategies for the formulation of multi-dimensional aggregates of suitably activated poly-topic porphyrins, without the use of metal ion connectors. The major part of the discussion relates to open porphyrinic networks supported by cooperative halogen bonding and hydrogen bonding interaction synthons, highlighting the crystal-engineering toolbox available to this end.

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“…Metal insertion and the anchored electron-withdrawing groups to the periphery of the porphyrin macrocycle reveal the better NLO behavior, possibly due to the enhancement of a well-known phenomenon for metalloporphyrins, the π−π aggregation. 97,98 This reflects the better nonlinear optical parameters (β, n 2 , σ TPA , χ (3) , etc.) of βdisubstituted and mono-benzo porphyrins compared to the other porphyrins reported from the last few years (see Table 4).…”

Section: ■ Results and Discussionmentioning

confidence: 95%

Unsymmetrically β-Functionalized π-Extended Porphyrins: Synthesis, Spectral, Electrochemical Redox Properties, and Their Utilization as Efficient Two-Photon Absorbers

et al. 2022

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Two new series of unsymmetrically β-functionalized porphyrins, MTPP(NO 2 )MA (1M), (MA = methyl acrylate) and MTPP(NO 2 )MB (2M) (MB = mono-benzo) (where M = 2H, Co(II), Ni(II), Cu(II) and Zn(II)), were synthesized and characterized by various spectroscopic techniques. The saddle shape conformation of ZnTPP(NO 2 )MAPy and ZnTPP(NO 2 )MB was confirmed by single-crystal X-ray analysis. Density functional theory (DFT) calculation revealed that NiTPP(NO 2 )MB has a severe nonplanar geometry possessing a high magnitude of ΔC β = ±0.727 Å and Δ24 = ±0.422 Å values among all other porphyrins. Synthesized β-substituted porphyrins exhibited red-shifted B-and Q-bands corresponding to their parent molecule due to the electron-withdrawing peripheral substituents. Notable redshift (Δλ max = 50−60 nm) in electronic spectral features and with weakintensity emission spectral features were observed for the free-base porphyrins and Zn(II) complexes compared to H 2 TPP and ZnTPP, respectively. The first-ring reduction potential of MTPP(NO 2 )MA (1M) exhibited 0.21−0.5 V anodic shift, whereas 0.18− 0.23 V anodic shift was observed in the first-ring oxidation potential compared to the corresponding MTPPs due to the presence of electron-withdrawing β-substituents at the periphery of the macrocycle. Interestingly, NiTPP(NO 2 )MA (1Ni) has shown an additional Ni II /Ni III oxidation potential observed at 2.05 V along with two ring-centered oxidations. The first-ring reduction and oxidation potentials of MTPP(NO 2 )MB (2M) have shown 0.39−0.46 and 0.19−0.27 V anodic shifts with respect to their corresponding MTPPs. The nonlinear optical (NLO) properties of all of the porphyrins were investigated, and the extracted nonlinear optical parameters revealed intense reverse-saturable absorption (RSA) behavior and the self-focusing behavior with positive nonlinear refractive index in the range of (0.19−1.75) × 10 −17 m 2 /W. Zn(II) complexes exhibited the highest two-photon absorption coefficient (β) and cross section (σ TPA ) of ∼95 × 10 −12 m/W and 19.66 × 10 4 GM, respectively, among all of the metal complexes.

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Ultrafast and short pulse optical nonlinearities of meso-tetrakis-(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl) porphyrin and its metal complexes

Cited by 31 publications

References 39 publications

An insight into phenomenal optical non‐linearities arising from synergistic relationship between selected BODIPYs and noble metal nanoparticles

An insight into phenomenal optical non‐linearities arising from synergistic relationship between selected BODIPYs and noble metal nanoparticles

Porphyrin-based assemblies directed by non-covalent interactions: highlights of recent investigations

Unsymmetrically β-Functionalized π-Extended Porphyrins: Synthesis, Spectral, Electrochemical Redox Properties, and Their Utilization as Efficient Two-Photon Absorbers

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