scholarly journals Helmet Phthalocyaninato Iron Complex as a Primary Drier for Alkyd Paints

Materials ◽  
2021 ◽  
Vol 14 (5) ◽  
pp. 1220
Author(s):  
Jan Honzíček ◽  
Eliška Matušková ◽  
Štěpán Voneš ◽  
Jaromír Vinklárek
Keyword(s):  
Catalytic Performance ◽  
Mechanical Tests ◽  
Iron Complex ◽  
Kinetic Measurements ◽  
Time Resolved ◽  
Strong Activity ◽  
Vis Spectroscopy ◽  
Order Of Magnitude ◽  
Transparent Coatings ◽  
Time Resolved Infrared Spectroscopy

This study describes the catalytic performance of an iron(III) complex bearing a phthalocyaninato-like ligand in two solvent-borne and two high-solid alkyd binders. Standardized mechanical tests revealed strong activity, which appeared in particular cases at concentrations about one order of magnitude lower than in the case of cobalt(II) 2-ethylhexanoate, widespread used in paint-producing industry. The effect of the iron(III) compound on autoxidation process, responsible for alkyd curing, was quantified by kinetic measurements by time-resolved infrared spectroscopy and compared with several primary driers. Effect of the drier concentration on coloration of transparent coatings was determined by UV–Vis spectroscopy.

scholarly journals Time-Resolved Infrared Spectroscopy of Binuclear Rhenium (I) Polypyridyl Complexes in Solution

1999 ◽  
Vol 19 (1-4) ◽  
pp. 279-282 ◽  
Author(s):  
L. C. Abbott ◽  
C. J. Arnold ◽  
K. C. Gordon ◽  
R. E. Hester ◽  
J. N. Moore ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Difference Spectra ◽  
Kinetic Measurements ◽  
Time Resolved ◽  
Bridging Ligand ◽  
Ligand Charge Transfer ◽  
Complex Forms ◽  
Time Resolved Infrared Spectroscopy ◽  
State Kinetic ◽  
Mlct State

A series of four binuclear rhenium (I) complexes of the general form [Re(CO)3Cl]2BL, where BL is a polypyridyl bridging ligand, have been studied using ultrafast time-resolved UV/visible (TRVIS) and infrared (TRIR) spectroscopies. Visible excitation produces a metal-to-ligand charge-transfer (MLCT) excited state. Kinetic measurements show that the lifetime of this MLCT state varies between 100 and 1900 ps, depending on the structure of the bridging ligand. TRIR difference spectra show that each complex forms a similar MLCT state which has mixed valence character.

scholarly journals Modified Ferrocenes as Primary Driers for Formulations of Alkyd Paints

Coatings ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 873
Author(s):  
Jan Honzíček ◽  
Tatiana Fedorova ◽  
Jaromír Vinklárek ◽  
Tomáš Mikysek ◽  
Ivana Císařová
Keyword(s):  
Catalytic Activity ◽  
Sampling Technique ◽  
Mechanical Tests ◽  
Attenuated Total Reflectance ◽  
X Ray Diffraction ◽  
Ferrocene Derivatives ◽  
Time Resolved ◽  
Alkyd Resins ◽  
Improved Performance ◽  
Time Resolved Infrared Spectroscopy

The effect of modification of benzoylferrocene periphery on catalytic activity toward drying of alkyd resins has been investigated by the combination of experimental techniques. A series of substituted ferrocenes have been synthesized and characterized by analytical and spectroscopic tools including X-ray diffraction analysis on single crystals. The electrochemical behavior of the ferrocene derivatives has been elucidated by cyclic voltammetry and rotation disk voltammetry. The activity toward room temperature curing of alkyd resin has been evaluated by standard mechanical tests on coated plates, which enabled to establish a structure/catalytic activity relationship. Fast drying of test coatings has been observed for formulations of (3-methoxybenzoyl) ferrocene. Time-resolved infrared spectroscopy in combination with attenuated total reflectance sampling technique enabled to reveal the kinetic origin of the improved performance for this ferrocene derivative.

Ferrocenium Ions as Catalysts: Decomposition Studies and Counteranion Influence on Catalytic Activity

Synthesis ◽  
2020 ◽  
Author(s):  
Eike B. Bauer ◽  
Kellsie Jurkowski
Keyword(s):  
Catalytic Activity ◽  
Stable Complex ◽  
Hydroxyl Groups ◽  
Test Reaction ◽  
Time Resolved ◽  
Vis Spectroscopy ◽  
Negative Effect ◽  
Order Of Magnitude ◽  
Catalyst Systems ◽  
Ferrocenium Cation

AbstractCatalyst decomposition has a negative effect on catalytic activity, and knowledge of decomposition pathways can assist with catalyst development. Ferrocenium cations have been employed as catalysts in a number of organic transformations, and we investigated the stability of a number of ferrocenium salts in solution. The observed rate decomposition constants for [Fc]Cl, [Fc]PF6, [Fc]BF4, [Fc]CSA [Fc = ferrocenium, CSA = camphor-10-sulfonate (β)], [AcFc]SbF6, (AcFc = acetylated ferrocene), and [FcB(OH)2]SbF6 [FcB(OH)2 = ferrocenylboronic acid] were determined in CH2Cl2 solution by time-resolved UV-vis spectroscopy. The rate decomposition constants depended on the nature of the counterion, with [Fc]Cl being the most stable complex in solution. The decomposition rate constants dropped by roughly an order of magnitude in most cases when the experiments were performed in nitrogenated solvent, demonstrating that the decomposition is mainly an oxidative process. The cosolvent HFIP (1,1,1,3,3,3-hexafluoropropan-2-ol) slowed the decomposition of the ferrocenium cations as well. Many catalytic or stoichiometric reactions of ferrocenium cations are performed with alcohols; we determined that hexan-1-ol is decomposed over the course of 16 hours, but not oxidized in the presence of a ferrocenium cation. Finally, the different ferrocenium cations were employed in a test reaction to determine catalytic activity. The nucleophilic substitution of hydroxyl groups in a tertiary propargylic alcohol by an alcohol is catalyzed by all complexes, and, again, a counterion dependency of the catalytic activity was observed. Also, HFIP increases the catalytic activity of the ferrocenium cations. The research has importance in the development of ferrocenium-based catalyst systems, because changes in the counterion as well as the architecture of the ferrocenium cation have an influence on stability and catalytic activity.

The Character of Low-Lying Excited States of Mixed-Ligand Metal Carbonyls. TD-DFT and CASSCF/CASPT2 Study of [W(CO)4L] (L = ethylenediamine, N,N'-dialkyl-1,4-diazabutadiene) and [W(CO)5L] (L = pyridine, 4-cyanopyridine)

2003 ◽  
Vol 68 (1) ◽  
pp. 89-104 ◽  
Author(s):  
Stanislav Záliš ◽  
Antonín Vlček ◽  
Chantal Daniel
Keyword(s):  
Excited States ◽  
Substitution Effect ◽  
Electronic Transitions ◽  
Ligand Field ◽  
Metal Carbonyls ◽  
Electron Density Redistribution ◽  
Time Resolved ◽  
Model Complex ◽  
Td Dft ◽  
Time Resolved Infrared Spectroscopy

This contribution presents the results of the TD-DFT and CASSCF/CASPT2 calculations on [W(CO)4(MeDAB)] (MeDAB = N,N'-dimethyl-1,4-diazabutadiene), [W(CO)4(en)] (en = ethylenediamine), [W(CO)5(py)] (py = pyridine) and [W(CO)5(CNpy)] (CNpy = 4-cyanopyridine) complexes. Contrary to the textbook interpretation, calculations on the model complex [W(CO)4(MeDAB)] and [W(CO)5(CNpy)] show that the lowest W→MeDAB and W→CNpy MLCT excited states are immediately followed in energy by several W→CO MLCT states, instead of ligand-field (LF) states. The lowest-lying excited states of [W(CO)4(en)] system were characterized as W(COeq)2→COax CT excitations, which involve a remarkable electron density redistribution between axial and equatorial CO ligands. [W(CO)5(py)] possesses closely-lying W→CO and W→py MLCT excited states. The calculated energies of these states are sensitive to the computational methodology used and can be easily influenced by a substitution effect. The calculated shifts of [W(CO)4(en)] stretching CO frequencies due to excitation are in agreement with picosecond time-resolved infrared spectroscopy experiments and confirm the occurrence of low-lying M→CO MLCT transitions. No LF electronic transitions were found for either of the complexes studied in the region up to 4 eV.

scholarly journals A diffusion anisotropy descriptor links morphology effects of H-ZSM-5 zeolites to their catalytic cracking performance

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Xiaoliang Liu ◽  
Jing Shi ◽  
Guang Yang ◽  
Jian Zhou ◽  
Chuanming Wang ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Catalytic Cracking ◽  
Catalytic Performance ◽  
Zeolite Catalysts ◽  
Time Resolved ◽  
Cracking Performance ◽  
Morphology Effect ◽  
Ft Ir ◽  
The Difference ◽  
Dynamics Simulations

AbstractZeolite morphology is crucial in determining their catalytic activity, selectivity and stability, but quantitative descriptors of such a morphology effect are challenging to define. Here we introduce a descriptor that accounts for the morphology effect in the catalytic performances of H-ZSM-5 zeolite for C4 olefin catalytic cracking. A series of H-ZSM-5 zeolites with similar sheet-like morphology but different c-axis lengths were synthesized. We found that the catalytic activity and stability is improved in samples with longer c-axis. Combining time-resolved in-situ FT-IR spectroscopy with molecular dynamics simulations, we show that the difference in catalytic performance can be attributed to the anisotropy of the intracrystalline diffusive propensity of the olefins in different channels. Our descriptor offers mechanistic insight for the design of highly effective zeolite catalysts for olefin cracking.

A quantum cascade laser setup for studying irreversible photoreactions in H2O with nanosecond resolution and microlitre consumption

2020 ◽  
Vol 22 (45) ◽  
pp. 26459-26467
Author(s):  
Jessica L. Klocke ◽  
Tilman Kottke
Keyword(s):  
Infrared Spectroscopy ◽  
Quantum Cascade Laser ◽  
Time Resolved ◽  
Quantum Cascade ◽  
Time Resolved Infrared Spectroscopy ◽  
Laser Setup

Flavin photoreduction in H2O is elucidated by developing a quantum cascade laser setup for time-resolved infrared spectroscopy on irreversible reactions.

scholarly journals Ultrafast proton release reaction and primary photochemistry of phycocyanobilin in solution observed with fs-time-resolved mid-IR and UV/Vis spectroscopy

2021 ◽  
Author(s):  
Maximilian Theiß ◽  
Merten Grupe ◽  
Tilman Lamparter ◽  
Maria Andrea Mroginski ◽  
Rolf Diller
Keyword(s):  
Density Functional ◽  
Transient Absorption ◽  
Vibrational Analysis ◽  
Density Functional Theory Calculations ◽  
Chem Phys ◽  
Molecular Structures ◽  
Ir Absorption ◽  
Time Resolved ◽  
Time Constants ◽  
Vis Spectroscopy

AbstractDeactivation processes of photoexcited (λex = 580 nm) phycocyanobilin (PCB) in methanol were investigated by means of UV/Vis and mid-IR femtosecond (fs) transient absorption (TA) as well as static fluorescence spectroscopy, supported by density-functional-theory calculations of three relevant ground state conformers, PCBA, PCBB and PCBC, their relative electronic state energies and normal mode vibrational analysis. UV/Vis fs-TA reveals time constants of 2.0, 18 and 67 ps, describing decay of PCBB*, of PCBA* and thermal re-equilibration of PCBA, PCBB and PCBC, respectively, in line with the model by Dietzek et al. (Chem Phys Lett 515:163, 2011) and predecessors. Significant substantiation and extension of this model is achieved first via mid-IR fs-TA, i.e. identification of molecular structures and their dynamics, with time constants of 2.6, 21 and 40 ps, respectively. Second, transient IR continuum absorption (CA) is observed in the region above 1755 cm−1 (CA1) and between 1550 and 1450 cm−1 (CA2), indicative for the IR absorption of highly polarizable protons in hydrogen bonding networks (X–H…Y). This allows to characterize chromophore protonation/deprotonation processes, associated with the electronic and structural dynamics, on a molecular level. The PCB photocycle is suggested to be closed via a long living (> 1 ns), PCBC-like (i.e. deprotonated), fluorescent species.

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