@article{GabrieldeAssis2024b,

title = {Preparation and Characterization of a Disilylated Naphthalenediimide Molecular Crystal: Perspectives for Organosilica Mesoporous Materials},

author = {Renan Gabriel de Assis and Marcos de Oliveira Junior and Márcia Tsuyama Escote and Carlos Basílio Pinheiro and José Javier Sáez Acuña and Fabio Furlan Ferreira and Luana Sucupira Pedroza and Sergio Brochsztain and Thiago Branquinho de Queiroz},

url = {https://pubs.acs.org/doi/full/10.1021/acsaenm.4c00341},

doi = {10.1021/acsaenm.4c00341},

issn = {2771-9545},

year  = {2024},

date = {2024-07-26},

urldate = {2024-07-26},

journal = {ACS Appl. Eng. Mater.},

volume = {2},

number = {7},

pages = {1976--1986},

publisher = {American Chemical Society (ACS)},

abstract = {Naphthalenetetracarboxylic diimides (NDIs) are efficient electron acceptors due to their high electron affinity. They are applied in heterogeneous catalysis and organic electronics. In this work, we report, for the first time, the synthesis of N,N′-bis[3-(triethoxysilyl)propyl]-1,4,5,8-naphthalenediimide (NDI-silane) as a molecular crystal obtained from recrystallization in petroleum ether. The compound is stable in air conditions and chloroform solution. Its crystal structure was determined by single-crystal X-ray diffraction. We have characterized the intermolecular dispersive interactions by density functional theory calculations, indicating that the stability of the crystal in air conditions is related to dispersive interactions. Furthermore, we characterize the optical and photoelectrical properties of thin NDI-silane films, demonstrating photoinduced conductivity over a wide range of temperatures (10–300 K). Remarkably, a venture of NDI-based organosilica can be obtained from stable NDI-silane crystals, prominent materials in organoelectronics and photocatalysis. As a proof of concept, we prepare mesoporous organosilicas with 100% NDI-silane using the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate as a templating and sol–gel catalytic agent. These materials show a well-formed organosilica network, presenting only T3 and T2 Si species, as probed by solid-state 29Si NMR. As a result, the mesoporous materials are considerably more resistant to thermal degradation than the crystals, being stable up to 450 °C. According to N2 adsorption isotherms and transmission electron microscopy images, they demonstrate microporous and mesoporous structures associated with narrow slitlike pores.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{GabrieldeAssis2024c,

title = {Preparation and Characterization of a Disilylated Naphthalenediimide Molecular Crystal: Perspectives for Organosilica Mesoporous Materials},

author = {Renan Gabriel de Assis and Marcos de Oliveira Junior and Márcia Tsuyama Escote and Carlos Basílio Pinheiro and José Javier Sáez Acuña and Fabio Furlan Ferreira and Luana Sucupira Pedroza and Sergio Brochsztain and Thiago Branquinho de Queiroz},

url = {https://pubs.acs.org/doi/full/10.1021/acsaenm.4c00341},

doi = {10.1021/acsaenm.4c00341},

issn = {2771-9545},

year  = {2024},

date = {2024-07-26},

urldate = {2024-07-26},

journal = {ACS Appl. Eng. Mater.},

volume = {2},

number = {7},

pages = {1976--1986},

publisher = {American Chemical Society (ACS)},

abstract = {Naphthalenetetracarboxylic diimides (NDIs) are efficient electron acceptors due to their high electron affinity. They are applied in heterogeneous catalysis and organic electronics. In this work, we report, for the first time, the synthesis of N,N′-bis[3-(triethoxysilyl)propyl]-1,4,5,8-naphthalenediimide (NDI-silane) as a molecular crystal obtained from recrystallization in petroleum ether. The compound is stable in air conditions and chloroform solution. Its crystal structure was determined by single-crystal X-ray diffraction. We have characterized the intermolecular dispersive interactions by density functional theory calculations, indicating that the stability of the crystal in air conditions is related to dispersive interactions. Furthermore, we characterize the optical and photoelectrical properties of thin NDI-silane films, demonstrating photoinduced conductivity over a wide range of temperatures (10–300 K). Remarkably, a venture of NDI-based organosilica can be obtained from stable NDI-silane crystals, prominent materials in organoelectronics and photocatalysis. As a proof of concept, we prepare mesoporous organosilicas with 100% NDI-silane using the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate as a templating and sol–gel catalytic agent. These materials show a well-formed organosilica network, presenting only T3 and T2 Si species, as probed by solid-state 29Si NMR. As a result, the mesoporous materials are considerably more resistant to thermal degradation than the crystals, being stable up to 450 °C. According to N2 adsorption isotherms and transmission electron microscopy images, they demonstrate microporous and mesoporous structures associated with narrow slitlike pores.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Morais2024b,

title = {Unraveling Interfacial Photoinduced Charge Transfer and Localization in CsPbBr3 Nanocrystals/Naphthalenediimide},

author = {Eliane A. Morais and Maykon A. Lemes and Natalilian R. S. Souza and Amando Siuiti Ito and Evandro L. Duarte and Ronaldo S. Silva and Sergio Brochsztain and J. A. Souza},

url = {https://pubs.acs.org/doi/10.1021/acsomega.4c01651},

doi = {10.1021/acsomega.4c01651},

issn = {2470-1343},

year  = {2024},

date = {2024-05-09},

urldate = {2024-05-09},

journal = {ACS Omega},

publisher = {American Chemical Society (ACS)},

abstract = {Halide perovskites have attracted much attention for energy conversion. However, efficient charge carrier generation, separation, and mobility remain the most important issues limiting the higher efficiency of solar cells. An efficient interfacial charge transfer process associated with exciton dynamics between all-inorganic CsPbBr3 nanocrystals and organic electron acceptors has been suggested. We observed a strong PL quenching of 78% in thin films when silane-functionalized naphthalenediimides (SNDI), used as electron-acceptors, are anchored on CsPbBr3 nanocrystals. Optical and structural characterizations confirm the charge transfer process without QDs degradation. The issue of whether these transferred charges are indeed available for utilization in solar cells remains uncertain. Our results reveal that the CsPbBr3 nanocrystals capped with these electron-acceptor SNDI molecules show a drastic increase in the electrical resistance and the absence of a photoconductivity effect. The results suggest charge transfer followed by strong localization of the charge carriers, preventing their extraction toward the electrodes of solar cell devices. We hope that this crucial aspect to attract attention and unveil a potential mechanism for charge delocalization, which could, in turn, lead to a groundbreaking enhancement in solar cell efficiency.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Morais2024c,

title = {Rashba Spin Splitting Limiting the Application of 2D Halide Perovskites for UV-Emitting Devices},

author = {Eliane A. Morais and Naidel A. M. S. Caturello and Maykon A. Lemes and Henrique Ferreira and Fabio F. Ferreira and Jose J. S. Acuña and Sergio Brochsztain and Gustavo M. Dalpian and J. A. Souza},

url = {https://pubs.acs.org/doi/abs/10.1021/acsami.3c16541},

doi = {10.1021/acsami.3c16541},

issn = {1944-8252},

year  = {2024},

date = {2024-01-24},

urldate = {2024-01-24},

journal = {ACS Appl. Mater. Interfaces},

volume = {16},

number = {3},

pages = {4261--4270},

publisher = {American Chemical Society (ACS)},

abstract = {Layered lead halide perovskites have attracted much attention as promising materials for a new generation of optoelectronic devices. To make progress in applications, a full understanding of the basic properties is essential. Here, we study 2D-layered (BA)2PbX4 by using different halide anions (X = I, Br, and Cl) along with quantum confinement. The obtained cell parameter evolution, supported by experimental measurements and theoretical calculations, indicates strong lattice distortions of the metal halide octahedra, breaking the local inversion symmetry in (BA)2PbCl4, which strongly correlates with a pronounced Rashba spin-splitting effect. Optical measurements reveal strong photoluminescence quenching and a drastic reduction in the PL quantum yield in this larger band gap compound. We suggest that these optical results are closely related to the appearance of the Rashba effect due to the existence of a local electric dipole. The results obtained in ab initio calculations showed that the (BA)2PbCl4 possesses electrical polarization of 0.13 μC/cm2 and spin-splitting energy of about 40 meV. Our work establishes that local octahedra distortions induce Rashba spin splitting, which explains why obtaining UV-emitting materials with high PLQY is a big challenge.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Morais2024d,

title = {Rashba Spin Splitting Limiting the Application of 2D Halide Perovskites for UV-Emitting Devices},

author = {Eliane A. Morais and Naidel A. M. S. Caturello and Maykon A. Lemes and Henrique Ferreira and Fabio F. Ferreira and Jose J. S. Acuña and Sergio Brochsztain and Gustavo M. Dalpian and Jose A. Souza},

url = {https://pubs.acs.org/doi/abs/10.1021/acsami.3c16541},

doi = {10.1021/acsami.3c16541},

issn = {1944-8252},

year  = {2024},

date = {2024-01-24},

urldate = {2024-01-24},

journal = {ACS Appl. Mater. Interfaces},

volume = {16},

number = {3},

pages = {4261--4270},

publisher = {American Chemical Society (ACS)},

abstract = {Layered lead halide perovskites have attracted much attention as promising materials for a new generation of optoelectronic devices. To make progress in applications, a full understanding of the basic properties is essential. Here, we study 2D-layered (BA)2PbX4 by using different halide anions (X = I, Br, and Cl) along with quantum confinement. The obtained cell parameter evolution, supported by experimental measurements and theoretical calculations, indicates strong lattice distortions of the metal halide octahedra, breaking the local inversion symmetry in (BA)2PbCl4, which strongly correlates with a pronounced Rashba spin-splitting effect. Optical measurements reveal strong photoluminescence quenching and a drastic reduction in the PL quantum yield in this larger band gap compound. We suggest that these optical results are closely related to the appearance of the Rashba effect due to the existence of a local electric dipole. The results obtained in ab initio calculations showed that the (BA)2PbCl4 possesses electrical polarization of 0.13 μC/cm2 and spin-splitting energy of about 40 meV. Our work establishes that local octahedra distortions induce Rashba spin splitting, which explains why obtaining UV-emitting materials with high PLQY is a big challenge.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{MartinsFreitas2023,

title = {Finite-Size Effects on Cs3Cu2I5 0D Electronic Nanostructures for Ultraviolet-Emitting Applications},

author = {Andre Luiz Martins Freitas and Aryane Tofanello and Fernando Pereira Sabino and Marissol Rodrigues Felez and Eliane Aparecida Morais and Sergio Brochsztain and Jose Javier Sáez Acuña and Gustavo Martini Dalpian and J. A. Souza},

url = {https://pubs.acs.org/doi/abs/10.1021/acsanm.3c00242},

doi = {10.1021/acsanm.3c00242},

issn = {2574-0970},

year  = {2023},

date = {2023-05-12},

urldate = {2023-05-12},

journal = {ACS Appl. Nano Mater.},

volume = {6},

number = {9},

pages = {7196--7205},

publisher = {American Chemical Society (ACS)},

abstract = {The potential to produce ultraviolet (UV) light-emitting devices has attracted significant interest in interdisciplinary fields, particularly in the use of 0D halide nanostructures due to their straightforward synthesis methods and exceptional efficiency in optoelectronics. Here, we present a systematic study involving nanostructure synthesis and significant changes in the electronic structure caused by finite-size effects. We have focused on the investigation of size effects on the UV-light emitting properties of all-inorganic Cs3Cu2I5 halide. We observe that bulk particles present a pronounced bright-blue emission at 440 nm with a high quantum yield of 80%. Very small quantum dots nanostructures (6–10 nm) reveal a significant shift of the photoluminescence peak down to ∼395 nm, close to the UV-A region, but with a quantum yield reduction of 10%. Surface engineering to obtain very small nanoparticles free from defects at the nanocrystal surface is crucial for maintaining a high quantum efficiency, allowing their use in UV-emitting devices.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{MartinsFreitas2023b,

title = {Finite-Size Effects on Cs3Cu2I5 0D Electronic Nanostructures for Ultraviolet-Emitting Applications},

author = {Andre Luiz Martins Freitas and Aryane Tofanello and Fernando Pereira Sabino and Marissol Rodrigues Felez and Eliane Aparecida Morais and Sergio Brochsztain and Jose Javier Sáez Acuña and Gustavo M. Dalpian and Jose Antonio Souza},

url = {https://pubs.acs.org/doi/abs/10.1021/acsanm.3c00242},

doi = {10.1021/acsanm.3c00242},

issn = {2574-0970},

year  = {2023},

date = {2023-05-12},

urldate = {2023-05-12},

journal = {ACS Appl. Nano Mater.},

volume = {6},

number = {9},

pages = {7196--7205},

publisher = {American Chemical Society (ACS)},

abstract = {The potential to produce ultraviolet (UV) light-emitting devices has attracted significant interest in interdisciplinary fields, particularly in the use of 0D halide nanostructures due to their straightforward synthesis methods and exceptional efficiency in optoelectronics. Here, we present a systematic study involving nanostructure synthesis and significant changes in the electronic structure caused by finite-size effects. We have focused on the investigation of size effects on the UV-light emitting properties of all-inorganic Cs3Cu2I5 halide. We observe that bulk particles present a pronounced bright-blue emission at 440 nm with a high quantum yield of 80%. Very small quantum dots nanostructures (6–10 nm) reveal a significant shift of the photoluminescence peak down to ∼395 nm, close to the UV-A region, but with a quantum yield reduction of 10%. Surface engineering to obtain very small nanoparticles free from defects at the nanocrystal surface is crucial for maintaining a high quantum efficiency, allowing their use in UV-emitting devices.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Marcon2022,

title = {Radical Anions and Dianions of Naphthalenediimides Generated within Layer-by-Layer Zirconium Phosphonate Thin Films},

author = {Rodrigo Oliveira Marcon and Jean-Jacques Bonvent and Sergio Brochsztain},

url = {https://pubs.acs.org/doi/abs/10.1021/acs.langmuir.1c03337},

doi = {10.1021/acs.langmuir.1c03337},

issn = {1520-5827},

year  = {2022},

date = {2022-02-15},

urldate = {2022-02-15},

journal = {Langmuir},

volume = {38},

number = {6},

pages = {2153--2161},

publisher = {American Chemical Society (ACS)},

abstract = {Chemical reduction of N,N′-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) with the reducing agent sodium dithionite gave stable colored reduced species, both in homogeneous solutions and in self-assembled thin films. When colorless PNDI aqueous solutions were titrated with the reducing agent, stepwise reduction was observed, giving first the radical anion (PNDI–•) and then the dianion (PNDI2–) species, which were detected by UV–visible–NIR spectroscopy, allowing the unambiguous determination of absorption maxima and molar absorptivities for each species. The radical anion PNDI–• was found to form π-dimers in water, but monomeric PNDI–• was formed in the presence of the cationic surfactant cetyltrimethylammonium bromide, indicating association with the micelles. Thin films of PNDI with 25 layers were grown by the zirconium phosphonate method on quartz substrates. Reduction of the films with sodium dithionite also produced radical anions and dianions of PNDI. However, reduction in the films was much slower than in solution, evidencing the compactness of the films. Moreover, reduction in the films did not proceed to completion, even with excess of the reducing agent, which can be attributed to the repulsion of negative charges within the film.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{deOliveiraMarcon2022,

title = {Stabilization of free radicals in layer-by-layer nanoarchitectures containing multiple arylenediimides},

author = {Rodrigo de Oliveira Marcon and Jean-Jacques Bonvent and Sergio Brochsztain},

url = {https://www.sciencedirect.com/science/article/abs/pii/S0143720821008147},

doi = {10.1016/j.dyepig.2021.109948},

issn = {0143-7208},

year  = {2022},

date = {2022-02-00},

urldate = {2022-02-00},

journal = {Dyes and Pigments},

volume = {198},

publisher = {Elsevier BV},

abstract = {Layer-by-layer thin films of arylenediimides were grown on phosphonate-primed silicon and quartz substrates by the zirconium phosphonate method. The method consists in depositing alternated organic/inorganic layers, where the organic layer was a phosphonate-substituted arylenediimide and the inorganic layer was Zr4+. Heterogeneous films with up to 50 layers, containing different imides, were produced. The building blocks were N,N′-bis(2-phosphonoethyl)pyromellitimide (PPMI), N,N′-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) and N,N′-bis(2-phosphonoethyl)-3,4,9,10-perylenediimide (PPDI). Thin films with the sequence PPDI/PNDI, PPDI/PPMI, PNDI/PPMI and PPDI/PNDI/PPMI were produced. Organized film growth was observed by UV–visible–NIR spectroscopy (quartz substrates) and ellipsometry (silicon substrates). AFM images showed that the surface of the films was smooth and uniform. The imides in the films were reduced using sodium dithionite as a reducing agent, generating stable radical anions and dianions of the imides. The following species were detected in the absorption spectra of the reduced films: PPDI−∙, PPDI2−, PNDI−∙, and PNDI2−. Reduction of the imides in the films was rather slow, as compared to homogeneous solutions. When the reduced films were exposed to atmospheric oxygen, reoxidation took place, which was also much slower than in homogeneous solutions. In conclusion, a mix of aromatic imide reduced species, absorbing through the whole visible range, was produced and stabilized in thin films.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Castanheira2022,

title = {Functionalized mesoporous silicas SBA-15 for heterogeneous photocatalysis towards CECs removal from secondary urban wastewater},

author = {Bruna Castanheira and Larissa Otubo and Cristiano L.P. Oliveira and Rosa Montes and José Benito Quintana and Rosario Rodil and Sergio Brochsztain and Vítor J.P. Vilar and Antonio Carlos S.C. Teixeira},

url = {https://www.sciencedirect.com/science/article/abs/pii/S0045653521024954},

doi = {10.1016/j.chemosphere.2021.132023},

issn = {0045-6535},

year  = {2022},

date = {2022-01-00},

urldate = {2022-01-00},

journal = {Chemosphere},

volume = {287},

publisher = {Elsevier BV},

abstract = {The photocatalytic activity of TiO2 nanoparticles (NPs) supported on mesoporous silica SBA-15 (TiO2/SBA-15) was evaluated for the photodegradation of sulfadiazine (SDZ), as target contaminant of emerging concern (CEC), using either pure water solutions (PW) or a real secondary urban wastewater (UWW) spiked with SDZ. For this purpose, TiO2/SBA-15 samples with 10, 20 and 30% TiO2 (w/w) were prepared by the sol-gel post synthetic method on pre-formed SBA-15, using titanium (IV) isopropoxide as a precursor. The TiO2/SBA-15 materials were characterized by HRTEM, SAXS and XRD, nitrogen adsorption isotherms and UV–vis diffuse reflectance spectroscopy. TiO2 NPs were shown to be attached onto the external surface, decorating the SBA-15 particles. The TiO2/SBA-15 catalysts were active in SDZ photodegradation using the annular FluHelik photoreactor, when irradiated with UVA light. The 30% TiO2/SBA-15 sample presented the best performance in optimization tests performed using PW, and it was further used for the tests with UWW. The photocatalytic activity of 30% TiO2/SBA-15 was higher (56% SDZ degradation) than that of standard TiO2–P25 (32% SDZ degradation) in the removal of SDZ spiked in the UWW ([SDZ] = 2 mg L−1). The photodegradation of SDZ with 30% TiO2/SBA-15 eached 90% for UWW spiked with a lower SDZ concentration ([SDZ] = 40 μg L−1). Aside of SDZ, a suit of 65 other CECs were also identified in the UWW sample using LC-MS spectrometry. A fast-screening test showed the heterogeneous photocatalytic system was able to remove most of the detected CECs from UWW, by either adsorption and/or photocatalysis.



},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Tosco2021,

title = {Layer-by-Layer Naphthalenediimide/Zn Phosphonate Hybrid Films Grown from Aqueous Solutions by a Simple Deposition Technique},

author = {Bruna Tosco and Barbra Poly-Anna Vera Melo and Daniel Hermida Merino and José Fernando Queiruga Rey and Sergio Brochsztain},

url = {https://pubs.acs.org/doi/abs/10.1021/acs.langmuir.0c03555},

doi = {10.1021/acs.langmuir.0c03555},

issn = {1520-5827},

year  = {2021},

date = {2021-02-23},

urldate = {2021-02-23},

journal = {Langmuir},

volume = {37},

number = {7},

pages = {2494--2502},

publisher = {American Chemical Society (ACS)},

abstract = {Hybrid thin films containing N,N′-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (PNDI) and zinc cations (PNDI/Zn films) were built on silicon and indium tin oxide (ITO) substrates by a simple layer-by-layer deposition process. Silicon substrates primed with a layer of phosphonate groups were immersed alternately into zinc nitrate and PNDI aqueous solutions, yielding PNDI/Zn films containing up to 40 layers. ITO substrates, on the other hand, were used without priming, and the deposition sequence began with a PNDI layer. All film growth steps were conducted at room temperature, using aqueous solutions, thus assuring an environmentally clean process. The PNDI/Zn films were studied by X-ray reflectivity and grazing angle X-ray diffraction, using synchrotron radiation source. The films were constituted by crystallites, containing zinc phosphonate layers oriented nearly parallel to the substrate. PNDI/Zn films on ITO were reduced to stable free radicals, which were observed by UV–visible spectroscopy. Moreover, PNDI/Zn bulk materials with structural analogy with the films were produced.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Andrade2021,

title = {Novel periodic mesoporous organosilicas containing pyromellitimides and their application for the photodegradation of asphaltenes},

author = {Luana dos Santos Andrade and Larissa Otubo and Bruna Castanheira and Sergio Brochsztain},

url = {https://www.sciencedirect.com/science/article/abs/pii/S138718112030740X},

doi = {10.1016/j.micromeso.2020.110740},

issn = {1387-1811},

year  = {2021},

date = {2021-01-00},

urldate = {2021-01-00},

journal = {Microporous and Mesoporous Materials},

volume = {312},

publisher = {Elsevier BV},

abstract = {Periodic mesoporous organosilicas containing pyromellitic diimide units embedded in the pore walls (PMOPMI) were synthesized by co-condensation of the bridged silsesquioxane precursor N,N′-bis(3-triethoxysilylpropyl)pyromellitimide with tetraethoxysilane (TEOS) in acidic conditions, in the presence of the structure-directing agent Pluronics P-123. PMOPMI were also synthesized from the corresponding amic acid precursors. The PMOPMI were studied by different techniques, including N2 adsorption isotherms, transmission electron microscopy, infrared and diffuse reflectance spectroscopy and contact angles. The studied samples displayed well-organized 2D-hexagonal structures. The PMOPMI were able to adsorb petroleum asphaltenes from toluene solutions, and were efficient photosensitizers for the photodegradation of the adsorbed asphaltenes when irradiated. Most of the asphaltenes were removed from solutions by the combined action of adsorption and photodegradation processes.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}