Article
Chemistry, Inorganic & Nuclear
William Crisp, Stephon Amadis Fagan-Avery, Brandon M. Campbell, Daniel R. Morphet, Kristopher G. Reynolds, Bryan Kudisch, Miguel I. Gonzalez, Shao-Liang Zheng, Dilek K. Dogutan, Daniel G. Nocera
Summary: The crystal structures of Mn(III)Cl and Pd(II) meso-(4-fluoro-2,6-dimethyl-phenyl) porphyrins have been synthesized and characterized. These homologous series of porphyrins, along with their Zn(II) counterpart, exhibit the manifestation of d-d states and spin-orbit coupling in the excited state dynamics of metalloporphyrins.
INORGANIC CHEMISTRY COMMUNICATIONS
(2022)
Article
Materials Science, Multidisciplinary
M. M. Makhlouf, M. M. Shehata
Summary: This study investigated the effect of introducing metal ion (Zn2+) into the center cavity of macrocyclic meso-tetra(4-pyridyl)porphine, H2TPyP, on its spectroscopic features, showing perturbations in the absorption spectroscopy of H2TPyP due to Zn complexation. The values of optical band gaps increased and dispersion parameters exhibited an increase in their values due to the insertion of Zn atom into H2TPyP. Nonlinear optical parameters such as third-order susceptibility, nonlinear refractive index, and nonlinear absorption coefficient showed a decrease in their values for ZnTPyP films compared to H2TPyP films.
Article
Chemistry, Physical
J. M. S. Lopes, A. E. H. Machado, A. A. Batista, P. T. Araujo, N. M. Barbosa Neto
Summary: This study presents a new pathway for generating hexaprotonated porphyrins through excited-state absorption, and reveals the formation of a new species during this process. The results show that the photo-protonation mechanism is driven by oxi-reduction reactions catalyzed by the porphyrin itself. Spectroscopic analysis further demonstrates that the emission lifetimes of the pristine and hexaprotonated porphyrins are quenched by chloride ions.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2022)
Article
Physics, Multidisciplinary
Angel L. Corps, Armando Relano
Summary: This study discusses a broad class of excited-state quantum phase transitions that lead to two different excited-state quantum phases, where equilibrium expectation values crucially depend on a specific conserved quantity in one phase, while energy is the only relevant thermodynamic magnitude in the other phase. The operator in the first phase acts as a discrete symmetry with two different eigenvalues.
PHYSICAL REVIEW LETTERS
(2021)
Article
Spectroscopy
Lucas F. Sciuti, Leticia D. Costa, Samuel Guieu, Leandro H. Z. Cocca, Bernardo A. Iglesias, Cleber R. Mendonca, Augusto C. Tome, M. Amparo F. Faustino, Leonardo De Boni
Summary: The absorption and relaxation dynamics of electronic states of porphyrins with b-(2,2-difluoro-1,3,2-dioxaborinin-5-yl) group were investigated in this study. The singlet-triplet conversion was quantified in free-base and Zn(II) porphyrins, while Co(II) and Cu(II) porphyrins showed relaxation back to the ground state only by internal conversion processes. Heavy atoms in Co(II) and Cu(II) seemed to prohibit radiative and intersystem crossing processes.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2021)
Article
Chemistry, Multidisciplinary
Svetlana Shostak, Woojin Park, Juwon Oh, Jinseok Kim, Seunghoon Lee, Hyeongwoo Nam, Michael Filatov, Dongho Kim, Cheol Ho Choi
Summary: The excited-state aromatization dynamics in the photochemical ring opening of DHA was investigated using nonadiabatic molecular dynamics simulations and the mixed-reference spin-flip (MRSF)-TDDFT method. It was found that the ring opening occurs in the excited state through a series of steps with increasing aromaticity. The competition between Baird and anti-Baird channels suggests that the quantum yield of the photochemical products can be controlled by tipping their balance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Victor M. Freixas, Alexander J. White, Tammie Nelson, Huajing Song, Dmitry Makhov, Dmitrii Shalashilin, Sebastian Fernandez-Alberti, Sergei Tretiale
Summary: This study compares three popular methods for large chromophores: Ehrenfest, surface hopping, and multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). The comparisons reveal method performance for population relaxation and coherent vibronic dynamics. The numerical convergence of MCE-AIMC algorithms is also studied to provide helpful reference data for selecting an optimal methodology for simulating excited-state molecular dynamics.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Victor Manuel Freixas, Sergei Tretiak, Sebastian Fernandez-Alberti
Summary: Progress in organic synthesis allows the exploration of diverse molecules with new structural topologies. The recently synthesized infinitene is a helically twisted figure-eight molecule with unique optoelectronic properties suitable for applications in nanoelectronics and photonics. However, the photophysical properties of infinitene have not been investigated.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
J. M. S. Lopes, A. E. H. Machado, A. A. Batista, B. A. Iglesias, P. T. Araujo, N. M. Barbosa Neto
Summary: Excited state absorption (ESA) has been used to controllably induce photo-protonation of porphyrins in chloroform solution. The number of fluorine atoms linked to the porphyrin's outlying phenyl substituents affects both the protonation formation rate and stability of the photo-protonated structures. Increasing the number of fluorine atoms decreases the efficiency of the reaction and reduces the stability of the photo-protonated porphyrins. These findings provide insights into tuning the ESA-triggered photo-protonation of porphyrins.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Giovanni Batignani, Emanuele Mai, Giuseppe Fumero, Shaul Mukamel, Tullio Scopigno
Summary: This article introduces a nonlinear Raman experiment to access an elusive aspect of the excited-state displacements: their sensed directions relative to the ground-state.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Yiwen Wang, Zehua Chen, Yang Yang
Summary: Modeling and interpreting vibrational spectra are important for studying reaction dynamics. This study presents a new method using excited state constrained minimized energy surfaces (CMESs) to describe vibrational excited state absorptions. Results from various model systems show that this method provides good estimations of transition frequencies for vibrational excited state absorptions, surpassing conventional harmonic approximations using potential energy surfaces.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Inorganic & Nuclear
Kamilla M. Alves, Joao Honorato, Luciano M. Liao, Vivianne S. Velozo-Sa, Adriana P. M. Guedes, Jocely de L. Dutra, Alejando P. Ayalla, Javier Ellena, Alzir A. Batista, Pablo J. Goncalves
Summary: This study synthesized, characterized, and tested the cytotoxicity of four new palladium/pyridylporphyrin complexes. The complexes showed selective indexes close to 1.2 against breast cancer cells, and interacted moderately with CT-DNA through hydrogen bonding, π-π stacking, and electrostatic interactions.
DALTON TRANSACTIONS
(2021)
Article
Spectroscopy
Ziheng Qiu, Jie Wei, Duoduo Li, Jinyou Long, Song Zhang, Bing Zhang
Summary: Femtosecond time-resolved photoelectron spectroscopy was used to investigate the ultrafast non-adiabatic dynamics of diethylamine (DEA). The study revealed that DEA undergoes internal conversion from the direct excitations to the 3p Rydberg states to the 3s state, followed by the breaking of the N-H bond. The non-adiabatic relaxation of the 3s state of DEA is predominantly characterized by the N-H bond dissociation process.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2022)
Article
Chemistry, Multidisciplinary
Pallas Chou, Lauren Kim, Sammer M. Marzouk, Rui Sun, Alaina C. Hartnett, Dilek K. Dogutan, Shao-Liang Zheng, Daniel G. Nocera
Summary: Zn(II), Cu(II), and Ni(II) 5,10,15,20-tetrakis(4-fluoro-2,6-dimethylphenyl)porphyrins (TFPs) were synthesized and characterized. The catalytic activity of Cu(II)TFP for the hydrogen evolution reaction (HER) was observed, and the mechanism of the reaction was determined by analyzing the voltammograms.
Article
Chemistry, Multidisciplinary
Haoyu Jing, Sijia Liu, Jianbing Jiang, Vy-Phuong Tran, Jie Rong, Pengzhi Wang, Jonathan S. Lindsey
Summary: The ability to synthesize synthetic analogues of native bacteriochlorophylls has diverse applications. A new method involving dimerization of a dihydrodipyrrin-acetal has been used to produce a range of new bacteriochlorins, including meso-bromobacteriochlorin intermediates and target bacteriochlorins.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Physical
Leandro H. Zucolotto Cocca, Andre Pelosi, Lucas F. Sciuti, Luis M. G. Abegao, Kenji Kamada, Sandrine Piguel, Cleber Renato Mendonca, Leonardo De Boni
Summary: Imidazopyridine derivatives, as unnatural purine isosteres, have attracted considerable attention due to their wide applicability in various scientific fields. They can be used as fluorescent bioprobes for DNA or RNA spectroscopic studies, and their optical properties can be enhanced by incorporating different structures in the central imidazopyridine scaffold. The research revealed high fluorescence quantum yields and two-photon absorption effects in certain imidazopyridine derivatives, indicating their potential as fluorescent probes induced by two-photon excitation.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Physical
Lucas F. Sciuti, Luis M. G. Abegao, Carlos H. D. dos Santos, Leandro H. Zucolotto Cocca, Rafaela G. M. da Costa, Jones Limberger, Lino Misoguti, Cleber R. Mendonca, Leonardo De Boni
Summary: The search for optical materials, especially organic compounds, is crucial for developing photonic devices and applications. This article proposes an alternative method to obtain the dispersion of the first-order hyperpolarizability using one- and two-photon absorption techniques, and predicts the dispersion of the first-order hyperpolarizability through spectral analysis.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Diego S. Manoel, Andre G. Pelosi, Leandro H. Zucolotto Cocca, Gustavo F. B. Almeida, Lucas F. Sciuti, Ruben D. F. Rodriguez, Luizmar Adriano Junior, Rosa S. Lima, Caridad Noda-Perez, Felipe T. Martins, Marcio A. R. Souza, Pablo J. Goncalves, Tertius L. Fonseca, Leonardo de Boni, Cleber R. Mendonca
Summary: Organic molecules with second and third-order nonlinear optical properties have various applications in optics and photonics. Terpenoid-like chalcones derivatives are a suitable choice for nonlinear optical materials due to their wide range of compounds that can be used in biophotonic applications. This study investigates the first-order molecular hyperpolarizability and two-photon absorption cross-section of several terpenoid-like chalcones derivatives, aiming for applications in the therapeutic window. Experimental and modeling methods were employed to gain insights into the properties and structure-relationship of these compounds.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2022)
Article
Agriculture, Multidisciplinary
Patricia Lima D'abadia, Amanda Fernandes Costa, Myllena Tolentino Firmino, Samantha Salomao Caramori, Ruy de Souza Lino-Junior, Fabiana Fonseca Zanoelo, Pablo Jose Goncalves, Luciane Almeida
Summary: The proteins in the H. speciosa latex are responsible for angiogenic activity, with enzymatic activity promoting wound healing processes. Despite low protein content, the enzymes in the serum fraction latex show significant potential for developing drugs with hypoallergenic responses.
BIOSCIENCE JOURNAL
(2022)
Article
Chemistry, Physical
Leandro Zucolotto H. Cocca, Andre Gasparotto Pelosi, Luis M. G. Abegao, Rafael de Q. Garcia, Jean-Christophe Mulatier, Delphine Pitrat, Cyrille Barsu, Chantal Andraud, Cleber R. Mendonca, Marcelo G. Vivas, Leonardo De Boni
Summary: Organic molecules, especially fluorene molecules, have been extensively studied for their photonics and biological applications due to their outstanding optical features. In this study, V and Y-shaped branching oligofluorenes containing multiple fluorene moieties were synthesized to enhance the nonlinear optical response. The relationship between the two-photon absorption (2PA) cross-section and the effective pi-electron number was investigated using femtosecond Z-scan spectroscopy and white light transient absorption spectroscopy (TAS).
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Organic
Delphine Naud-Martin, Marharyta Kosiuha, Leandro H. Zucolotto Cocca, Pascal Retailleau, Florence Mahuteau-Betzer, Leonardo De Boni, Sandrine Piguel
Summary: This study investigates a light-driven 3-component sulfonylation reaction of indolizines without requiring an external photocatalyst. Mechanistic investigations support the in situ formation of an electron donor-acceptor (EDA) complex. This transformation offers a mild and sustainable approach with high functional group tolerance for synthesizing 3-sulfonylated indolizines, which have valuable photophysical properties and potential applications in fluorescence-related fields.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Carlos H. D. dos Santos, Leandro Zucolotto H. Cocca, Andre Gasparotto Pelosi, Vasco F. Batista, Diana C. G. A. Pinto, M. Amparo F. Faustino, Marcelo G. Vivas, Jonathas de Paula Siqueira, Cleber R. Mendonca, Leonardo De Boni
Summary: The frequency-resolved first order molecular hyperpolarizability (beta) of five new push-pull cinnamylidene acetophenone derivatives was determined using femtosecond laser-induced Hyper-Rayleigh Scattering (HRS). Significant increase in beta values was observed in molecules, particularly in regions near the two-photon resonance mediated by electron withdrawing and donating groups. This effect was mapped using wavelength-tunable femtosecond Z-scan technique and modeled based on the sum-over-states approach for the second- and third-order nonlinearities. The results suggest a strategy to obtain large beta values mediated by the 2PA transition.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Joao V. P. Valverde, Andre G. Pelosi, Leandro H. Zucolotto Cocca, Orlando D. Marbello, Julie le Bescont, Chloe Breton-Patient, Sandrine Piguel, Daniel L. Silva, Leonardo De Boni, Cleber R. Mendonca
Summary: In this study, spectroscopic measurements were conducted on seven imidazo[1,2-a]pyridine derivatives with different peripheral groups to investigate their influence on the two-photon absorption (2PA) cross-section. The results revealed that introducing a naphthalene substituent led to an approximately seven-fold increase in the 2PA cross-section, indicating the effective enhancement of molecular conjugation. Similarly, when groups with strong electron withdrawing or donating characteristics were linked to the imidazo[1,2-a]pyridine core, the same outcome was observed. These findings suggest a potential approach to achieving significant nonlinear optical responses in this class of organic compounds.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Physical
Eli Silveira-Alves Jr, Fabio C. Bezerra, Rubens A. Guerra, Nicholas Zufelato, Carolina S. Martins, Jaqueline C. Desordi, Anderson R. L. Caires, Andris F. Bakuzis, Pablo J. Goncalves
Summary: This study presents the coupling of cationic meso-tetrakis(N-methylpyridinium-4-yl) porphyrin (TMPyP) and its zinc complex (ZnTMPyP) with magnetic nanoparticles (MNPs) of manganese ferrite (MnFe2O4) covered with citric acid (CA), dimercaptosuccinic acid (DMSA), and tripolyphosphate (TPP). The binding interaction between porphyrins and MNPs was determined using the Stern-Volmer method, which was based on the properties of the coating layer and unfunctionalized metallic sites on the MNPs surface. It was found that the TNPP and CA MNPs showed higher binding constants (Kb) and the fluorescence emission and singlet oxygen production were reduced when the porphyrins were bound to MNPs.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Andre Gasparotto Pelosi, Eli Silveira-Alves Jr, Leandro Henrique Zucolotto Cocca, Joao Victor Valverde, Guilherme Roberto Oliveira, Daniel Luiz da Silva, Leonardo De Boni, Pablo Jose Goncalves, Cleber Renato Mendonca
Summary: This study investigates the impact of different electron-withdrawing and electron-donating groups on the linear and nonlinear optical properties of acetamide-chalcone derivatives. The addition of the dimethylamine group significantly enhances the fluorescence emission, making it suitable for biological applications. It also increases the two-photon absorption cross-section of the lower energy band. Quantum Chemistry Calculations (QCCs) and Sum-Over-States (SOS) approach are used to confirm the observed electronic states and model the experimental data.
Article
Materials Science, Multidisciplinary
Raiane S. Araujo, Lucas F. Sciuti, Leandro H. Z. Cocca, Thais O. Lopes, Aline A. Silva, Luis M. G. Abegao, Marcelo S. Valle, Jose J. Rodrigues Jr, Cleber R. Mendonca, Leonardo De Boni, Marcio A. R. C. Alencar
Summary: The NLO response of the investigated compounds is mainly determined by the length of the conjugated chain and the different functional groups. The replacement of the aromatic peripherals and the presence of bromo- and chloro-substituents do not greatly influence the NLO response.
Article
Optics
Francisco A. A. Santos, Carlos E. R. Cardoso, Jose J. Rodrigues Jr, Leonardo De Boni, Luis M. G. Abegao
Summary: Experimental nonlinear optics is expensive, but exploring the NLO responses of organic and inorganic compounds has opened new possibilities. This study simulated the beta values of 27 organic compounds using density functional theory and compared them with experimental analogs obtained by the Hyper-Rayleigh Scattering technique.
Article
Optics
Iouri Evgenievitch Borissevitch, Eli Silveira-Alves Jr, Claudio Gabriel Lemos Almeida, Guilherme Rocha Lino Souza, Svyatoslav Sergeevich Sokolov, Pablo Jose Goncalves
Summary: The excited triplet state of a molecule (T-1) is an important intermediate product in photochemical reactions and its quantum yield (phi(T)) is a crucial characteristic in studying these reactions. Determining the phi(T) value is particularly significant in the search for effective photosensitizers used in photodynamic therapy (PDT). This study analyzes the effect of laser pulse intensity on calculating the phi(T) value using the Laser Flash Photolysis technique and determines the phi(T) values for different photosensitizers. The obtained results are highly compatible with values obtained through other methods.
Article
Engineering, Multidisciplinary
Iouri E. Borissevitch, Pablo J. Goncalves, Lucimara P. Ferreira, Alexey A. Kostyukov, Vladimir A. Kuzmin
Summary: The quantum yields (fT) and energies (ET) of the first triplet state (T1) were investigated for four cyanine dye molecules with two chromophores (BCDs) in 1-propanol solutions. These BCDs have potential applications as photosensitizers in photodynamic therapy (PDT) and fluorescence diagnostics (FD). The heterocycle structure connecting the chromophores plays a crucial role in electron tunneling efficiency, which can be characterized by the splitting of the BCD triplet energy levels. Increasing the tunneling efficiency was found to decrease ET values and increase fT values, indicating the potential synthesis of new effective photosensitizers based on cyanine dyes for various applications, including photodynamic therapy.
