scholarly journals Comparative Experimental and Theoretical Study of Mg, Al and Zn Aryloxy Complexes in Copolymerization of Cyclic Esters: The Role of the Metal Coordination in Formation of Random Copolymers

Polymers ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2273
Author(s):  
Ilya Nifant’ev ◽  
Pavel Komarov ◽  
Valeriya Ovchinnikova ◽  
Artem Kiselev ◽  
Mikhail Minyaev ◽  
...  
Keyword(s):  
Density Functional ◽  
Rational Design ◽  
Qualitative Difference ◽  
Random Copolymers ◽  
Coordination Polymerization ◽  
Polymer Backbone ◽  
Catalytic Behavior ◽  
Cyclic Esters ◽  
Dft Modeling ◽  
The Density Functional Theory

Homogeneity of copolymers is a general problem of catalytic coordination polymerization. In ring-opening polymerization of cyclic esters, the rational design of the catalyst is generally applied to solve this problem by the equalization of the reactivities of comonomers—however, it often leads to a reduction of catalytic activity. In the present paper, we studied the catalytic behavior of BnOH-activated complexes (BHT)Mg(THF)2nBu (1), (BHT)2AlMe (2) and [(BHT)ZnEt]2 (3), based on 2,6-di-tert-butyl-4-methylphenol (BHT-H) in homo- and copolymerization of L-lactide (lLA) and ε-caprolactone (εCL). Even at 1:5 lLA/εCL ratio Mg complex 1 catalyzed homopolymerization of lLA without involving εCL to the formation of the polymer backbone. On the contrary, Zn complex 3 efficiently catalyzed random lLA/εCL copolymerization; the presence of mono-lactate subunits in the copolymer chain clearly pointed to the transesterification mechanism of copolymer formation. Both epimerization and transesterification side processes were analyzed using the density functional theory (DFT) modeling that confirmed the qualitative difference in catalytic behavior of 1 and 3: Mg and Zn complexes demonstrated different types of preferable coordination on the PLA chain (k2 and k3, respectively) with the result that complex 3 catalyzed controlled εCL ROP/PLA transesterification, providing the formation of lLA/εCL copolymers that contain mono-lactate fragments separated by short oligo(εCL) chains. The best results in the synthesis of random lLA/εCL copolymers were obtained during experiments on transesterification of commercially available PLLA, the applicability of 3/BnOH catalyst in the synthesis of random copolymers of εCL with methyl glycolide, ethyl ethylene phosphonate and ethyl ethylene phosphate was also demonstrated.

scholarly journals DFT Visualization and Experimental Evidence of BHT-Mg-Catalyzed Copolymerization of Lactides, Lactones and Ethylene Phosphates

Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1641 ◽  
Author(s):  
Ilya Nifant’ev ◽  
Andrey Shlyakhtin ◽  
Maxim Kosarev ◽  
Dmitry Gavrilov ◽  
Stanislav Karchevsky ◽  
...  
Keyword(s):  
Ring Opening ◽  
Density Functional ◽  
Point Of View ◽  
Basis Set ◽  
Random Copolymers ◽  
Key Factors ◽  
Functional Theory ◽  
Cyclic Esters ◽  
Dft Modeling ◽  
Derivatives Of

Catalytic ring-opening polymerization (ROP) of cyclic esters (lactides, lactones) and cyclic ethylene phosphates is an effective way to process materials with regulated hydrophilicity and controlled biodegradability. Random copolymers of cyclic monomers of different chemical nature are highly attractive due to their high variability of characteristics. Aryloxy-alkoxy complexes of non-toxic metals such as derivatives of 2,6-di-tert-butyl-4-methylphenoxy magnesium (BHT-Mg) complexes are effective coordination catalysts for homopolymerization of all types of traditional ROP monomers. In the present paper, we report the results of density functional theory (DFT) modeling of BHT-Mg-catalyzed copolymerization for lactone/lactide, lactone/ethylene phosphate and lactide/ethylene phosphate mixtures. ε-Caprolactone (ε-CL), l-lactide (l-LA) and methyl ethylene phosphate (MeOEP) were used as examples of monomers in DFT simulations by the Gaussian-09 program package with the B3PW91/DGTZVP basis set. Both binuclear and mononuclear reaction mechanistic concepts have been applied for the calculations of the reaction profiles. The results of calculations predict the possibility of the formation of random copolymers based on l-LA/MeOEP, and substantial hindrance of copolymerization for ε-CL/l-LA and ε-CL/MeOEP pairs. From the mechanistic point of view, the formation of highly stable five-membered chelate by the products of l-LA ring-opening and high donor properties of phosphates are the key factors that rule the reactions. The results of DFT modeling have been confirmed by copolymerization experiments.

scholarly journals DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

Polymers ◽  
2019 ◽  
Vol 11 (12) ◽  
pp. 2078 ◽  
Author(s):  
Ilya Nifant’ev ◽  
Pavel Ivchenko
Keyword(s):  
Ring Opening ◽  
Density Functional ◽  
Comparative Modeling ◽  
Ring Opening Polymerization ◽  
Proton Exchange ◽  
Dft Methods ◽  
Experimental Proof ◽  
Cyclic Esters ◽  
Dft Modeling

Organocatalysis is highly efficient in the ring-opening polymerization (ROP) of cyclic esters. A variety of initiators broaden the areas of organocatalysis in polymerization of different monomers, such as lactones, cyclic carbonates, lactides or gycolides, ethylene phosphates and phosphonates, and others. The mechanisms of organocatalytic ROP are at least as diverse as the mechanisms of coordination ROP; the study of these mechanisms is critical in ensuring the polymer compositions and architectures. The use of density functional theory (DFT) methods for comparative modeling and visualization of organocatalytic ROP pathways, in line with experimental proof of the structures of the reaction intermediates, make it possible to establish these mechanisms. In the present review, which continues and complements our recent manuscript that focused on DFT modeling of coordination ROP, we summarized the results of DFT modeling of organocatalytic ROP of cyclic esters and some related organocatalytic processes, such as polyester transesterification.

scholarly journals Rational Design of Donor Acceptor Based Semiconducting Copolymers with High Dielectric Constant

2020 ◽  
Author(s):  
Aiswarya Abhisek Mohapatra ◽  
Yifan Dong ◽  
Puttaraju Boregowda ◽  
Ashutosh Mohanty ◽  
Aditya Sadhanala ◽  
...  
Keyword(s):  
Dielectric Constant ◽  
Organic Semiconductors ◽  
Density Functional ◽  
Rational Design ◽  
Dielectric Constants ◽  
Side Chains ◽  
Free Charge ◽  
Coulombic Interaction ◽  
Polymer Backbone ◽  
Donor Acceptor

<div> <div> <div> <p>An efficient photogeneration of free charge carriers has long been recognized as the paramount challenge in organic photovoltaic (OPV) devices. The low dielectric constant organic semiconductors fall short to reduce strong Coulombic interaction of tightly bound exciton and hence lead to a loss mechanism in OPVs due to charge-carrier recombination. To circumvent this problem, we adopt a strategy to enhance the dielectric constant of organic semiconductors by incorporating tetraethyleneglycol (TEG) side-chains. We report synthesis of three new semiconducting copolymers by combining thiophene substituted diketopyrrolopyrrole (TDPP) monomer with three other monomeric units with varying electron donating strength: benzodithiophene (BBT-3TEG-TDPP), TDPP (TDPP-3TEG-TDPP) and naphthalene diimide (PNDITEG-TDPP). BBT-3TEG-TDPP and PNDITEG-TDPP showed highest dielectric constants (~ 5) at 1MHz frequency suggesting efficient contribution of dipolar polarization from TEG side-chains. To understand the electronic contribution of the polymer backbone and the polarity of TEG side-chains, and the resulting enhancement of the dielectric constant, we further performed first-principles density functional theory calculations. Single-component organic solar cells (OSC) fabricated utilizing these polymers resulted in poor performance which is attributed to the absence of free charge generation. Furthermore, transient absorption spectroscopy studies show low exciton diffusion length as observed in donor-acceptor type conjugated polymers. Our results suggest that, the strategy of enhancing dielectric constant with polar side-chains is not sufficient to reduce Coulombic interaction between hole and electron in OSCs. </p> </div> </div> </div>

scholarly journals Rational Design of Donor Acceptor Based Semiconducting Copolymers with High Dielectric Constant

2020 ◽  
Author(s):  
Aiswarya Abhisek Mohapatra ◽  
Yifan Dong ◽  
Puttaraju Boregowda ◽  
Ashutosh Mohanty ◽  
Aditya Sadhanala ◽  
...  
Keyword(s):  
Dielectric Constant ◽  
Organic Semiconductors ◽  
Density Functional ◽  
Rational Design ◽  
Dielectric Constants ◽  
Side Chains ◽  
Free Charge ◽  
Coulombic Interaction ◽  
Polymer Backbone ◽  
Donor Acceptor

<div> <div> <div> <p>An efficient photogeneration of free charge carriers has long been recognized as the paramount challenge in organic photovoltaic (OPV) devices. The low dielectric constant organic semiconductors fall short to reduce strong Coulombic interaction of tightly bound exciton and hence lead to a loss mechanism in OPVs due to charge-carrier recombination. To circumvent this problem, we adopt a strategy to enhance the dielectric constant of organic semiconductors by incorporating tetraethyleneglycol (TEG) side-chains. We report synthesis of three new semiconducting copolymers by combining thiophene substituted diketopyrrolopyrrole (TDPP) monomer with three other monomeric units with varying electron donating strength: benzodithiophene (BBT-3TEG-TDPP), TDPP (TDPP-3TEG-TDPP) and naphthalene diimide (PNDITEG-TDPP). BBT-3TEG-TDPP and PNDITEG-TDPP showed highest dielectric constants (~ 5) at 1MHz frequency suggesting efficient contribution of dipolar polarization from TEG side-chains. To understand the electronic contribution of the polymer backbone and the polarity of TEG side-chains, and the resulting enhancement of the dielectric constant, we further performed first-principles density functional theory calculations. Single-component organic solar cells (OSC) fabricated utilizing these polymers resulted in poor performance which is attributed to the absence of free charge generation. Furthermore, transient absorption spectroscopy studies show low exciton diffusion length as observed in donor-acceptor type conjugated polymers. Our results suggest that, the strategy of enhancing dielectric constant with polar side-chains is not sufficient to reduce Coulombic interaction between hole and electron in OSCs. </p> </div> </div> </div>

scholarly journals Regulating the absorption spectrum of polydopamine

2020 ◽  
Vol 6 (36) ◽  
pp. eabb4696 ◽  
Author(s):  
Yuan Zou ◽  
Xiaofeng Chen ◽  
Peng Yang ◽  
Guijie Liang ◽  
Ye Yang ◽  
...  
Keyword(s):  
Light Absorption ◽  
Density Functional ◽  
Rational Design ◽  
Complex Structure ◽  
Photothermal Effect ◽  
Absorption Property ◽  
Functional Theory ◽  
Solar Desalination ◽  
The Density Functional Theory ◽  
Donor Acceptor

Polydopamine (PDA) has been increasingly exploited as an advanced functional material, and its emergent light absorption property plays a crucial role in determining various utilizations. However, the rational design and efficient regulation of PDA absorption property remain a challenge due to the complex structure within PDA. In this work, we propose a facile method to regulate the light absorption behaviors of PDA by constructing donor-acceptor pairs within the microstructures through the chemical connections between indoledihydroxy/indolequinone and their oligomers with 2,2,6,6-tetramethylpiperidine-1-oxyl moiety. The detailed structural and spectral analysis, as well as the density functional theory simulation, further confirms the existence of donor-acceptor molecular pair structures, which could decrease the energy bandgap and increase the electron delocalization for enhancing light absorption across a broad spectrum. These rationally designed PDA nanoparticles with tunable absorption properties also show improved total photothermal effect and demonstrate excellent performances in solar desalination.

scholarly journals Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Molecules ◽  
2019 ◽  
Vol 24 (22) ◽  
pp. 4117 ◽  
Author(s):  
Ilya Nifant’ev ◽  
Pavel Ivchenko
Keyword(s):  
Ring Opening ◽  
Density Functional ◽  
Transition States ◽  
Ring Opening Polymerization ◽  
Molecular Structures ◽  
Data Sets ◽  
Dft Methods ◽  
Cyclic Esters ◽  
Dft Modeling ◽  
The Difference

Ring-opening polymerization (ROP) of cyclic esters (lactones, lactides, cyclic carbonates and phosphates) is an effective tool to synthesize biocompatible and biodegradable polymers. Metal complexes effectively catalyze ROP, a remarkable diversity of the ROP mechanisms prompted the use of density functional theory (DFT) methods for simulation and visualization of the ROP pathways. Optimization of the molecular structures of the key reaction intermediates and transition states has allowed to explain the values of catalytic activities and stereocontrol events. DFT computation data sets might be viewed as a sound basis for the design of novel ROP catalysts and cyclic substrates, for the creation of new types of homo- and copolymers with promising properties. In this review, we summarized the results of DFT modeling of coordination ROP of cyclic esters. The importance to understand the difference between initiation and propagation stages, to consider the possibility of polymer–catalyst coordination, to figure out the key transition states, and other aspects of DFT simulation and visualization of ROP have been also discussed in our review.

scholarly journals SYNTHESIS, CHARACTERIZATION, DFT MODELING AND IN VITRO ANTIMYCOBACTERIAL ACTIVITY ASSAYS OF A SILVER(I)-ISONIAZID COMPLEX

Química Nova ◽  
2020 ◽  
Author(s):  
José Paris Junior ◽  
Maurício Cavicchioli ◽  
Rachel Machado ◽  
Fernando Pavan ◽  
Douglas Hideki Nakahata ◽  
...  
Keyword(s):  
Density Functional ◽  
Antimycobacterial Activity ◽  
Nitrate Anion ◽  
Functional Theory ◽  
Bidentate Coordination ◽  
Anion Coordination ◽  
Dft Modeling ◽  
The Density Functional Theory ◽  
Strain H37rv

In the present work, a silver(I) complex with the antimycobacterial drug isoniazid (inh) is described. Elemental and thermogravimetric analyses confirmed a 1:1 metal:ligand ratio for the silver-isoniazid (Ag-inh) complex with molecular composition AgC6H7N3O·NO3. Infrared (IR) analysis suggests a bidentate coordination of isoniazid to silver by the nitrogen of the NH2 group and by the oxygen of the C=O group, and also confirms the presence of free nitrate anion. Coordination by the NH2 group was reinforced by NMR measurements. Computational simulations using the density functional theory (DFT) reinforced that the ligand coordinates to the silver atom by the NH2 and C=O groups. The silver complex presented a minimal inhibitory concentration (MIC90) of 0.78 μg/mL against the standard Mycobacterium tuberculosis strain H37Rv. The data reported herein warrants further investigation on Ag-inh complex as a potential agent against tuberculosis.

scholarly journals Regulating the Electron Localization of Metallic Bismuth for Boosting CO2 Electroreduction

2021 ◽  
Vol 14 (1) ◽  
Author(s):  
Dan Wu ◽  
Renfei Feng ◽  
Chenyu Xu ◽  
Peng-Fei Sui ◽  
Jiujun Zhang ◽  
...  
Keyword(s):  
Density Functional ◽  
Rational Design ◽  
Reaction Pathway ◽  
Highly Active ◽  
Mechanistic Pathway ◽  
The Density Functional Theory ◽  
Co2 Electroreduction ◽  
Metallic Bismuth ◽  
Local Electronic Structure ◽  
Positive Valence

AbstractElectrochemical reduction of CO2 to formate is economically attractive but improving the reaction selectivity and activity remains challenging. Herein, we introduce boron (B) atoms to modify the local electronic structure of bismuth with positive valence sites for boosting conversion of CO2 into formate with high activity and selectivity in a wide potential window. By combining experimental and computational investigations, our study indicates that B dopant differentiates the proton participations of rate-determining steps in CO2 reduction and in the competing hydrogen evolution. By comparing the experimental observations with the density functional theory, the dominant mechanistic pathway of B promoted formate generation and the B concentration modulated effects on the catalytic property of Bi are unravelled. This comprehensive study offers deep mechanistic insights into the reaction pathway at an atomic and molecular level and provides an effective strategy for the rational design of highly active and selective electrocatalysts for efficient CO2 conversion.

scholarly journals The Contribution of Density Functional Theory to the Atomistic Knowledge of Electrochromic Processes

Molecules ◽  
2021 ◽  
Vol 26 (19) ◽  
pp. 5793
Author(s):  
Bruna Clara De Simone ◽  
Marta Erminia Alberto ◽  
Tiziana Marino ◽  
Nino Russo ◽  
Marirosa Toscano
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Rational Design ◽  
Computational Studies ◽  
Redox Potentials ◽  
Experimental Characterization ◽  
Excitation Energies ◽  
Functional Theory ◽  
Physico Chemical ◽  
The Density Functional Theory

In this review, we provide a brief overview of the contribution that computational studies can offer to the elucidation of the electronic mechanisms responsible for the electrochromism phenomenon, through the use of the density functional theory (DFT) and its time-dependent formulation (TDDFT). Although computational studies on electrochromic systems are not as numerous as those for other physico-chemical processes, we will show their reliability and ability to predict structures, excitation energies, and redox potentials. The results confirm that these methods not only help in the interpretation of experimental data but can also be used for the rational design of molecules with interesting electrochromic properties to be initiated for synthesis and experimental characterization.

scholarly journals Case Study in a Conceptual DFT Investigation of New Corrosion Inhibitor

2021 ◽  
Vol 11 (4) ◽  
pp. 4007-4015
Keyword(s):  
Molecular Orbital ◽  
Density Functional ◽  
Basis Set ◽  
Functional Theory ◽  
Dft Modeling ◽  
Highest Occupied Molecular Orbital ◽  
The Density Functional Theory ◽  
Modeling Techniques ◽  
Lowest Unoccupied Molecular Orbital

Inhibition efficiency of thiosemicarbazide derivative, namely 4-ethyl-1-(4-oxo-4-phenylbutanoyl)thiosemicarbazide (EOPT) on corrosion of mild steel, was investigated utilizing the density functional theory (DFT) modeling techniques in the aqueous phase. Chemical parameters at the quantum level, such as energies of highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), dipole moment (µ), absolute electronegativity (χ), global hardness (η), softness (σ), and the fraction of electrons transferred (∆N) have been determined at the B3LYP level of theory with 6-31G (d, p) basis set.

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