Self-assembled organic nanostructures and nonlinear optical properties of heteroleptic corrole–phthalocyanine europium triple-decker complexes

Lu, Guifen; Li, Jing; Yan, Sen; He, Cheng; Shi, Mengying; Zhu, Weihua; Ou, Zhongping; Kadish, Karl M.

doi:10.1016/j.dyepig.2015.05.008

Cited by 31 publications

(23 citation statements)

References 49 publications

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“…Following these clues, considerable efforts have been expended to the fabrications of CCs having high third-order NLO susceptibilities, originated from their promising technological applications in data storage, optical limiting, all-optical switching, optical communications, optical computing, and so on . In this context, the reported examples include heterothiometallic clusters, , polyoxometalate (POM)-based hybrids, POM-Schiff base-based hybrids, POM-phthalocyanine- and POM-porphyrin-based hybrids, as well as sandwich-type phthalocyaninato lanthanide (Ln) complexes …”

Section: Introductionmentioning

confidence: 99%

Multifunctional Dy^III Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate N,N,N-Pincer Ligands

Cui

Yang

et al. 2021

Inorg. Chem.

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By utilizing Dy(hfac)3(H2O)2 to react with enantiomerically pure tridentate N,N,N-pincer ligands, namely (−)/(+)-2,6-bis(4′,5′-pinene-2′-pyridyl)pyridine (L R and L S ), respectively, homochiral DyIII enantiomeric pairs formulated as Dy(hfac)3L R /Dy(hfac)3L S (R -1/S -1) (hfac– = hexafluoroacetylacetonate) were achieved and structurally characterized. Meanwhile, their magnetic, photoluminescent (PL), and chiroptical properties were probed. The PL test results indicate that the precursor Dy(hfac)3(H2O)2 only shows very weak emission, while R -1 exhibits characteristic DyIII f–f transition emission bands at room temperature. Furthermore, the nonlinear optical responses of Dy(hfac)3(H2O)2, L R /L S , and R -1/S -1 were investigated in detail based on crystalline samples. The results reveal that L R and L S present the coexistence of second- and third-harmonic generation (SHG and THG) responses with more intense signals for SHG responses; and Dy(hfac)3(H2O)2 merely displays weak THG responses, while R -1 and S -1 also only exhibit THG responses. However, the THG intensities of R -1 and S -1 are more than six times larger than that of Dy(hfac)3(H2O)2 under the identical measurement conditions. These results demonstrate that introducing homochiral N,N,N-pincer ligands to replace two H2O molecules of Dy(hfac)3(H2O)2 results in significant improvements of both PL performances and THG responses of resultant R -1/S -1 enantiomers. R -1 and S -1 integrate PL, THG, and chiral optical activity in one molecule, suggesting their multifunctional merits. In particular, a convenient method is introduced to simultaneously test THG and SHG responses of molecular materials based on crystalline samples in this work.

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Section: Introductionmentioning

confidence: 99%

Multifunctional Dy^III Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate N,N,N-Pincer Ligands

Cui

Yang

et al. 2021

Inorg. Chem.

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“…The properties of phthalocyanines in photodynamic therapy (PDT) are influenced by the structure of central metal cation . As mentioned earlier, phthalocyanines have been used in many areas, and the most important of these is their use as photosensitizing agents in photodynamic therapy …”

Section: Introductionmentioning

confidence: 99%

7‐Oxy‐3,4‐cyclohexenecoumarin Carrying Novel Zinc(II) and Indium(III) Acetate Phthalocyanines: Synthesis, Characterization, Photophysical and Photochemical Properties

et al. 2019

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In this study, 7‐hydroxy‐3,4‐cyclohexenecoumarin (1), two new phthalonitriles, 7‐(2,3‐dicyanophenoxy)‐3,4‐cyclohexene‐coumarin (2), 7‐(3,4‐dicyanophenoxy)‐3,4‐cyclohexenecoumarin (3), were prepared. The phthalonitrile derivatives 2 and 3 were converted to the respective non‐peripheral tetra, peripheral tetra 7‐oxy‐3,4‐cyclohexenecoumarin substituted zinc(II) (4,6) and indium(III)acetate phthalocyanine (5,7) derivatives. All novel purified compounds (2‐7) were characterized by elemental analysis, FT‐IR, UV‐vis, 1H NMR, 13C NMR, MALDI‐TOF mass data. The spectral, photophysical (fluorescence quantum yields and lifetimes), and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of the synthesized Pcs (4‐7) were studied in DMF, and the results were compared to determine the effects of the locations of substituents and the diversity of the central metal atom on these properties. The 7‐oxy‐3,4‐cyclohexenecoumarin bearing phthalocyaninatozinc(II) and indium(III)acetate complexes showed good solubility in organic solvents such as chloroform, dichloromethane, tetrahydrofuran, acetone, DMF and DMSO. The fluorescence quenching behavior were investigated using 1,4‐benzoquinone as a quencher. They have an acceptable level of singlet oxygen production, which determines the usability of phthalocyanines in photodynamic therapy applications and demonstrated appropriate photodegradation. The thermal properties of Pcs (4‐7) were also investigated.

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“…[1][2][3][4][5][6][7][8][9][10] It has been suggested that lanthanide double-decker phthalocyaninates (LnPc 2 ,D D) show improvedo ptical nonlinearities because of their expanded pelectron system and the presence of the heavy lanthanide central metal, [11][12][13][14][15][16] which enhances the rate of intersystemc rossing (ISC) to the triplet state. [23][24][25] Unlike the DD counterparts, which are paramagnetic,t he positive chargeo nt he two Ln III ions in TD complexes balancest he negative chargei nt he three Pc ligands, thus improving the NLO behavior. [23][24][25] Unlike the DD counterparts, which are paramagnetic,t he positive chargeo nt he two Ln III ions in TD complexes balancest he negative chargei nt he three Pc ligands, thus improving the NLO behavior.…”

Section: Introductionmentioning

confidence: 99%

“…It has been suggested that lanthanide double‐decker phthalocyaninates (LnPc 2 , DD) show improved optical nonlinearities because of their expanded π‐electron system and the presence of the heavy lanthanide central metal, which enhances the rate of intersystem crossing (ISC) to the triplet state . A further increase in the number of decks from two to six has been shown to enhance optical‐limiting behavior, although these studies are still limited: in the case of triple‐decker sandwiches (Ln 2 Pc 3 , TD), only a few studies have been reported, including homoleptic trisphthalocyaninates and some heteroleptic complexes . Unlike the DD counterparts, which are paramagnetic, the positive charge on the two Ln III ions in TD complexes balances the negative charge in the three Pc ligands, thus improving the NLO behavior.…”

Section: Introductionmentioning

confidence: 99%

First Example of Nonlinear Optical Materials Based on Nanoconjugates of Sandwich Phthalocyanines with Quantum Dots

Oluwole

Yagodin

Mkhize

et al. 2017

Chemistry A European J

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We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A B-type phthalocyanine ligand (2,3-bis[2'-(2''-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker Eu octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.

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Self-assembled organic nanostructures and nonlinear optical properties of heteroleptic corrole–phthalocyanine europium triple-decker complexes

Cited by 31 publications

References 49 publications

Multifunctional Dy^III Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate N,N,N-Pincer Ligands

Multifunctional Dy^III Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate N,N,N-Pincer Ligands

7‐Oxy‐3,4‐cyclohexenecoumarin Carrying Novel Zinc(II) and Indium(III) Acetate Phthalocyanines: Synthesis, Characterization, Photophysical and Photochemical Properties

First Example of Nonlinear Optical Materials Based on Nanoconjugates of Sandwich Phthalocyanines with Quantum Dots

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Self-assembled organic nanostructures and nonlinear optical properties of heteroleptic corrole–phthalocyanine europium triple-decker complexes

Cited by 31 publications

References 49 publications

Multifunctional DyIII Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate N,N,N-Pincer Ligands

Multifunctional DyIII Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate N,N,N-Pincer Ligands

7‐Oxy‐3,4‐cyclohexenecoumarin Carrying Novel Zinc(II) and Indium(III) Acetate Phthalocyanines: Synthesis, Characterization, Photophysical and Photochemical Properties

First Example of Nonlinear Optical Materials Based on Nanoconjugates of Sandwich Phthalocyanines with Quantum Dots

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Multifunctional Dy^III Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate N,N,N-Pincer Ligands

Multifunctional Dy^III Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate N,N,N-Pincer Ligands