Effects of Progressive Halogen Substitution on the Photoluminescence Properties of an Erbium−Porphyrin Complex

Pizzoferrato, R.; Francini, R.; Pietrantoni, S.; Paolesse, Roberto; Mandoj, Federica; Monguzzi, Angelo; Meinardi, Francesco

doi:10.1021/jp9119183

Cited by 34 publications

(22 citation statements)

References 34 publications

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“…As discussed above, the configuration of the coordinated ligands, forced by their attachment to the macrocycle, leads to a different orientation of the donor atoms coordinated to the lanthanide (see Scheme ). As stated above, C–H as well as N–H vibrations will also contribute to the non‐radiative quenching of the Nd emission 29. The emission quantum yields reported herein are, however, comparable with those reported for other Nd complexes, such as a capped Ln‐monoporphyrin Nd(TPP)Tp ( Φ NIR =2.4×10 −3 ; Tp=hydridotris(1‐pyrazolyl)borate),30 a Nd 1,3‐diketonate complex31 and Nd III complexes coordinated to eosin, erythrosine32 or terpyridine‐boradiazaindacene derivatives 33…”

Section: Resultsmentioning

confidence: 92%

Metal‐Oxide Nanoparticles with Desired Morphology Inherited from Coordination‐Polymer Precursors

Zhao

Sun

et al. 2012

Chemistry A European J

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Efficient and designable strategies for fabrication of nanomaterials with controlled morphology are fundamentally important to nanotechnology development. A number of studies have shown that the morphology of nanomaterials, especially for semiconductors, determines the optical-electronic properties, band gap, photoenergy conversion efficiency, photocatalytic activities, and so forth.[1] Accordingly, various strategies based on physical and chemical methods have been developed in recent years for the fabrication of different kinds of nanomaterials. Chemical methods, such as solgel processes, micelles, chemical precipitation, hydrothermal synthesis, pyrolysis, and vapor deposition, have been frequently employed in the large-scale preparation of nanostructured materials. [2] Many nanostructured materials with uniform morphology and specific crystal planes have been successfully synthesized in recent years. For example, TiO 2 crystals with a high percentage of exposed {001} facets could be obtained with the aid of fluorine-containing compounds.[3] Hexagonal, platelike, ZnO nanocrystals with polar {001} facets were synthesized by changing the molar ratio of the reactants. [4] BiVO 4 nanoplates with the preferred (010) surface orientation have been prepared both in aqueous ethanolamine solution or in the presence of a directing agent.[5] Co 3 O 4 nanorods synthesized in an ethylene glycol solution predominantly exposed {110} planes.[6] Despite the versatile methods reported, fabrication of nanostructured materials with desirable morphology and composition still remains a big challenge and great interest in the field of material science.Herein, we report the fabrication of metal oxides with controlled morphology and crystal planes by using coordination-polymer nanoparticles (CPNs) as precursors based a on template-engaged-quasi-topotactic transformation by an "escape-by-crafty-scheme" strategy and the CPNs with designed morphology can be synthesized based on the soft chemical assembly of metal-ion precursors and organic coordination ligands at the molecular level (Scheme 1). Firstly, CPNs with well-defined morphology were synthesized by soft chemical assembly of the metal ion and ptcda. The morphology of the CPNs can be elaborately controlled by the judicious choice of synthesis conditions, such as temperature, organic additives, reactant concentration, metal ions, and so forth. Then the metal-oxide nanoparticles with maintained morphology were formed; even the crystal-plane orientation was inherited from the pristine CPNs, by a simple thermal treatment process. The CPNs act as precursors for the formation of nanostructured metal oxides with maintained morphology through a template-engaged-quasi-topotactic, transformation process. This strategy is demonstrated to be a general and convenient approach to prepare metaloxide nanomaterials with controlled morphology and crystal planes.The zinc-ion-based CPNs, Zn-ptcda, were synthesized through the reaction of ptcda with ZnA C H T U N G T R E N N U N G (OAc) 2 in a sol...

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Section: Resultsmentioning

confidence: 92%

Metal‐Oxide Nanoparticles with Desired Morphology Inherited from Coordination‐Polymer Precursors

Zhao

Sun

et al. 2012

Chemistry A European J

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“…UV–vis spectra of samples containing the free ligand TTP in DMF were taken. As shown in Figure b, the spectra exhibited the typical features of porphyrins, including the Soret band in the range of 420–460 nm and the corresponding weak Q‐bands at 500–650 nm . Compared to the free ligand spectrum, the spectra of the metal‐coordination complexes were different in two ways.…”

Section: Resultsmentioning

confidence: 97%

Metalloporphyrin Complex‐Based Nanosonosensitizers for Deep‐Tissue Tumor Theranostics by Noninvasive Sonodynamic Therapy

Chen

Cui

et al. 2018

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Metal complexes are widely used as anticancer drugs, while the severe side effects of traditional chemotherapy require new therapeutic modalities. Sonodynamic therapy (SDT) provides a significantly noninvasive ultrasound (US) treatment approach by activating sonosensitizers and initiating reactive oxygen species (ROS) to damage malignant tissues. In this work, three metal 4‐methylphenylporphyrin (TTP) complexes (MnTTP, ZnTTP, and TiOTTP) are synthesized and encapsulated with human serum albumin (HSA) to form novel nanosonosensitizers. These nanosonosensitizers generate abundant singlet oxygen (1O2) under US irradiation, and importantly show excellent US‐activatable abilities with deep‐tissue depths up to 11 cm. Compared to ZnTTP‐HSA and TiOTTP‐HSA, MnTTP‐HSA exhibits the strongest ROS‐activatable behavior due to the lowest highest occupied molecular orbital−lowest unoccupied molecular orbital gap energy by density functional theory. It is also effective for deep‐tissue photoacoustic/magnetic resonance dual‐modal imaging to trace the accumulation of nanoparticles in tumors. Moreover, MnTTP‐HSA intriguingly achieves high SDT efficiency for simultaneously suppressing the growth of bilateral tumors away from ultrasound source in mice. This work develops a deep‐tissue imaging‐guided SDT strategy through well‐defined metalloporphyrin nanocomplexes and paves a new way for highly efficient noninvasive SDT treatments of malignant tumors.

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“…Tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate)mono(2,2'-bipyridine) erbium(III), [Er(fod) 3 (bipy)], was obtained as follows: under stirring, a Hfod (3 mmol) methanol solution (20 ml) was added to a 1 mmol of Er(NO 3 )·5H 2 O in methanol. The mixture was neutralized by adding potassium methoxide (3 mmol) dropwise under vigorous stirring until potassium nitrate precipitated.…”

Section: Materials Synthesis and Analytical Datamentioning

confidence: 99%

“…The removal of solvent molecules can be efficiently achieved by the use of N,N-donor molecules: these ligands act as Lewis bases, and form adducts with tris β-diketonate complexes because of the tendency of the lanthanide ion to expand its coordination sphere and to achieve a coordination number higher than six (typically eight or nine). On the other hand, deuteration and halogenation of the ligands (i.e., the substitution of H atoms in the aromatic rings with halogens atoms such as fluorine [6][7][8], chlorine [9] and bromine [10]) has proven to be a successful approach for the second objective. Absorptions are diminished (C-D) or absent (C-F), because the third overtone of C-D is located at 1.5 µm and the third overtone of C-F at 2.6 µm.…”

Section: Introductionmentioning

confidence: 99%

“…In an attempt to simultaneously fulfill both requirements, we have designed two highly fluorinated erbium(III) complexes, with general formula [Er(fod) 3 (N,N-donor)], where fod corresponds to 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate and N,N-donor is either bipyridine (bipy) or bathophenantholine (bath): the introduction of N,N-donor molecules in the coordination sphere of Er 3+ excludes the effect of O-H oscillators and the use of a perfluorinated ligand (Hfod) minimizes the deleterious effect of C-H oscillators. In this article, we report their synthesis, structural elucidation by single crystal X-ray diffraction and semiempirical quantum chemistry calculations, and a thorough characterization by X-ray powder diffraction (XRPD), NMR, ATR-FTIR and Raman spectroscopies, DSC, absorption and photoluminescence studies.…”

Section: Introductionmentioning

confidence: 99%

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Highly fluorinated erbium(III) complexes for emission in the C-band

Martín-Ramos

Silva

Lahoz

et al. 2014

Journal of Photochemistry and Photobiology A: Chemistry

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Two highly fluorinated Er 3+ complexes with three 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5octanedionate (fod) groups and either bipyridine (bipy) or bathophenantholine (bath) as the ancillary ligand emitting at the C-band (third communication window for fiber transmission) are presented. These complexes are the result of a design process aimed at decreasing the vibrational quenching from high frequency oscillators. The structure of [Er(fod) 3 (bipy)] has been elucidated by single-crystal X-ray diffraction, while Sparkle/PM6 and Sparkle/PM7 semi-empirical calculations have been used to model the ground state geometry for [Er(fod) 3 (bath)]. Photoluminescence studies confirm sensitization of the Er 3+ ions by antenna effect, leading to NIR emission at 1.53 µm. This energy transfer proves to be more efficient for [Er(fod) 3 (bath)] as a result of the bulkier and more rigid structure of bath diimide. The good thermal stability of the materials up to over 200 ºC allows envisaging their use in erbium-doped waveguides, NIR-OLEDs or other optoelectronic devices.

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Effects of Progressive Halogen Substitution on the Photoluminescence Properties of an Erbium−Porphyrin Complex

Cited by 34 publications

References 34 publications

Metal‐Oxide Nanoparticles with Desired Morphology Inherited from Coordination‐Polymer Precursors

Metal‐Oxide Nanoparticles with Desired Morphology Inherited from Coordination‐Polymer Precursors

Metalloporphyrin Complex‐Based Nanosonosensitizers for Deep‐Tissue Tumor Theranostics by Noninvasive Sonodynamic Therapy

Highly fluorinated erbium(III) complexes for emission in the C-band

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