Excellent Nonlinear Optical Limiting Behavior of Tetra (C<sub>60</sub>) Lanthanum Phthalocyanine in Solid Poly(methyl methacrylate) Films

Xu, Rui; Zhu, Min; Li, Wei; Ding, Jiale; Zhang, Yunhe

doi:10.1021/acs.jpcc.2c07514

Cited by 5 publications

(4 citation statements)

References 41 publications

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“…In N 1 s core-level spectra, in the central panels of Figure 3 , three contributions can be discerned, the one due to the nitrogen atoms of the isoindole units coordinated to the metal ion (M-N iso , where M = Y, La, Gd and Tb and N iso = nitrogen atom of isoindole or unit) at a BE between 398.0 and 398.2 eV, the peak stemming from azomethine nitrogen (γ-N) bonded with carbon atoms C-N=C at a BE from 399.5.0 to 400.0 eV and the shake-up features around 401.0 and 401.6 eV [ 33 , 34 , 35 , 36 ]. Table S4 reports the binding energies of the different components identified in the fits.…”

Section: Resultsmentioning

confidence: 99%

Solvothermal Synthesis of Rare Earth Bisphthalocyanines

Bolivar-Pineda,

Mendoza-Domínguez,

Rudolf

et al. 2024

Molecules

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Rare earth bisphthalocyanines (MPc2) are of particular interest because of their behavior as single-molecular magnets, which makes them suitable for applications in molecular spintronics, high-density data storage and quantum computation. Nevertheless, MPc2 are not commercially available, and the synthesis routes are mainly focused on obtaining substituted phthalocyanines. Two preparation routes depend on the precursor: synthesis from phthalonitrile (PN) and the metalation of free or dilithium phthalocyanine (H2Pc and Li2Pc). In both options, byproducts such as free-base phthalocyanine and in the first route additional PN oligomers are generated, which influence the MPc2 yield. There are three preparation methods for these routes: heating, microwave radiation and reflux. In this research, solvothermal synthesis was applied as a new approach to prepare yttrium, lanthanum, gadolinium and terbium unsubstituted bisphthalocyanines using Li2Pc and the rare earth(III) acetylacetonates. Purification by sublimation gave high product yields compared to those reported, namely 68% for YPc2, 43% for LaPc2, 63% for GdPc2 and 62% for TbPc2, without any detectable presence of H2Pc. Characterization by infrared, Raman, ultraviolet–visible and X-ray photoelectron spectroscopy as well as elemental analysis revealed the main featuresof the four bisphthalocyanines, indicating the success of the synthesis of the complexes.

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Section: Resultsmentioning

confidence: 99%

Solvothermal Synthesis of Rare Earth Bisphthalocyanines

Bolivar-Pineda,

Mendoza-Domínguez,

Rudolf

et al. 2024

Molecules

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“…Furthermore, A–D–A type compounds 1–5 show a more excellent NLO property with higher β eff and Imχ (3) values than some reported materials (Table S11). ,− Thus, these compounds can be considered as promising OL materials in laser protection.…”

Section: Resultsmentioning

confidence: 99%

Structure–Property Relationships of ITIC-Based Acceptor–Donor–Acceptor Type Molecules as Novel Organic Nonlinear Optical Materials

Li,

Feng,

Liu

et al. 2023

ACS Appl. Opt. Mater.

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Organic π-conjugated molecules incorporating with an electron donor (D) and/or acceptor (A) have been extensively applied in nonlinear optical (NLO) fields. The efficient electron transfers and delocalization in the molecular backbone can boost the NLO behavior effectively. Thus, the rational constructions of D−A type π-conjugated structures are one of the key approaches to facilitate the development of organic NLO materials and their applications. Because of the unique structure characteristics, ITIC-based A−D−A type molecules are promising NLO materials. However, there is no report about ITIC-based molecules as NLO materials so far; furthermore, their structure−property relationships remain unclear. Herein, five ITIC-based A− D−A type molecules (1−5) incorporating different electron-rich/-poor groups in the electron-donating core or electronwithdrawing groups were designed and synthesized. Meanwhile, D−A type compound 6 with the "half-structure" of 1 was synthesized for comparison. The relationships of the structure and NLO property were studied by the theoretical calculations and Zscan experiments. Expectedly, these molecules exhibit an NLO response originating from reverse saturable absorption (RSA) to a nanosecond pulsed laser at 532 nm, which is attributed to the strong intramolecular D−A interaction and planar π-conjugated backbones of molecules. The A−D−A type compound 1 exhibits an excellent NLO property compared to compound 6. Compounds with smaller band gaps exhibit more excellent NLO properties. The structurally tunable nonlinear extinction coefficients of A−D−A type compounds increase from 70 to 162 cm GW −1 at the representative input laser energy of 10 μJ. The length of the alkyl chain bearing on the side of the conjugated backbone has a slight effect on their NLO behavior although it has a significant influence on the performances of organic field-effect transistors and organic solar cells. Because of the RSA behaviors, these compounds can be applied as optical limiting materials and show laser limiting thresholds varying from 12.3 to 3.6 J cm −2 . This work exploits a novel application of ITIC-based A−D−A type molecules in organic NLO fields and, more importantly, affords a prototype of structure− property relationships as a guideline for the rational development toward outstanding materials.

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“…Most notably, InOC-19 has a T min of 0.21, which is superior to most reported metal-cluster-based optical limiting materials and comparable to the best ones (Table S13). ,− In contrast to the benchmark OL materials of fullerenes, porphyrins, and derivatives, − which are all deep colored and have poor optical transparency, InOC-19 possesses superior optical transparency and OL performance. To better quantitatively evaluate the OL activities, the nonlinear absorption coefficient β (eqs –) in the Supporting Information were obtained with values of 0.33 × 10 –9 , 0.43 × 10 –9 , 0.54–10 –9 , 2.8 × 10 –9 , and 9.6 × 10 –9 m/W for InOC-15 to InOC-19 , respectively(Figure c).…”

Section: Optical Limiting Performancementioning

confidence: 99%

Sequential Aggregation of Heterometallic {M₄X₄}-Cubanes to Wheel-Shaped In₁₀Ni₈-Oxo Clusters for Optical Limiting Application

Sun

Zhang

et al. 2023

Chem. Mater.

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It is extremely challenging but critical to regulate the structural attributes and physicochemical behaviors of metaloxo clusters in a controllable manner. Connecting versatile building units and importing aromatic ligands into crystalline materials facilitates the construction of unprecedented structures and provides a platform for the interpretation of structure−activity relationships at the molecular level. In this work, the solvent effect and organic-ligand-induced effect are exploited to formulate and regulate the variety and connection modes of cuboidal {M 4 X 4 } building units (M= In, Ni; X= O, Cl) in a controlled and incremental fashion. Not only were the inorganic basic-cubane and its dimeric analogue isolated but also their hexameric aggregation into an In 10 Ni 8 -oxo cluster with a wheel-shaped architecture was realized with the assistance of aromatic carboxylates. The In 10 Ni 8 -oxo cluster presents the largest size record in the realm of InOCs, and its peripheral surface could be modified to modulate their corresponding physicochemical properties; in particular, the benzoate and naphthoate groups can bring in abundant π•••π stacking interactions. Based on the results of Z-scan third-order nonlinear optical (NLO) measurements, these clusters present high reverse saturable absorption (RSA) suitable as optical limiting (OL) materials and constitute an instructive comparison that the general trend of the OL effect is gradually enhanced with the accumulation of more {M 4 X 4 }-cubanes including heavy atoms as well as richer and stronger π•••π stacking interactions and better delocalization. This work not only starts the research on InOCs-based optical limiting materials but also provide strategies of regulating building units for constructing heterometallic clusters.

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Excellent Nonlinear Optical Limiting Behavior of Tetra (C₆₀) Lanthanum Phthalocyanine in Solid Poly(methyl methacrylate) Films

Cited by 5 publications

References 41 publications

Solvothermal Synthesis of Rare Earth Bisphthalocyanines

Solvothermal Synthesis of Rare Earth Bisphthalocyanines

Structure–Property Relationships of ITIC-Based Acceptor–Donor–Acceptor Type Molecules as Novel Organic Nonlinear Optical Materials

Sequential Aggregation of Heterometallic {M₄X₄}-Cubanes to Wheel-Shaped In₁₀Ni₈-Oxo Clusters for Optical Limiting Application

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Excellent Nonlinear Optical Limiting Behavior of Tetra (C60) Lanthanum Phthalocyanine in Solid Poly(methyl methacrylate) Films

Cited by 5 publications

References 41 publications

Solvothermal Synthesis of Rare Earth Bisphthalocyanines

Solvothermal Synthesis of Rare Earth Bisphthalocyanines

Structure–Property Relationships of ITIC-Based Acceptor–Donor–Acceptor Type Molecules as Novel Organic Nonlinear Optical Materials

Sequential Aggregation of Heterometallic {M4X4}-Cubanes to Wheel-Shaped In10Ni8-Oxo Clusters for Optical Limiting Application

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Product

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Excellent Nonlinear Optical Limiting Behavior of Tetra (C₆₀) Lanthanum Phthalocyanine in Solid Poly(methyl methacrylate) Films

Sequential Aggregation of Heterometallic {M₄X₄}-Cubanes to Wheel-Shaped In₁₀Ni₈-Oxo Clusters for Optical Limiting Application