scholarly journals Benchmarking computational methods and influence of guest conformation on chirogenesis in zinc porphyrin complexes

2020 ◽  
Vol 22 (19) ◽  
pp. 11025-11037
Author(s):  
Irina Osadchuk ◽  
Victor Borovkov ◽  
Riina Aav ◽  
Eric Clot
Keyword(s):  
Solvent Effect ◽  
Computational Methods ◽  
Zinc Porphyrin ◽  
Chiral Compounds ◽  
Zinc Porphyrins

Different computational methods and influence of the guest conformation and solvent effect to analyze chirogenesis in zinc porphyrins by several chiral compounds have been investigated.

Kinetic Solvent Effects in Organic Reactions

2017 ◽  
Author(s):  
Belinda Slakman ◽  
Richard West
Keyword(s):  
Solvent Effect ◽  
Reaction Kinetics ◽  
Computational Methods ◽  
High Throughput ◽  
Kinetic Modeling ◽  
Solvent Effects ◽  
Reaction Rates ◽  
Prior Work ◽  
Solvent Phase ◽  
High Throughput Manner

<div> <div> <div> <p>This article reviews prior work studying reaction kinetics in solution, with the goal of using this information to improve detailed kinetic modeling in the solvent phase. Both experimental and computational methods for calculating reaction rates in liquids are reviewed. Previous studies, which used such methods to determine solvent effects, are then analyzed based on reaction family. Many of these studies correlate kinetic solvent effect with one or more solvent parameters or properties of reacting species, but it is not always possible, and investigations are usually done on too few reactions and solvents to truly generalize. From these studies, we present suggestions on how best to use data to generalize solvent effects for many different reaction types in a high throughput manner. </p> </div> </div> </div>

Imine-substituted dipyrromethanes in the synthesis of porphyrins bearing one or two meso substituents

2005 ◽  
Vol 09 (08) ◽  
pp. 554-574 ◽  
Author(s):  
Masahiko Taniguchi ◽  
Arumugham Balakumar ◽  
Dazhong Fan ◽  
Brian E. McDowell ◽  
Jonathan S. Lindsey
Keyword(s):  
Zinc Acetate ◽  
Room Temperature ◽  
Vilsmeier Reaction ◽  
Materials Chemistry ◽  
Air Oxidation ◽  
Zinc Porphyrin ◽  
New Synthesis ◽  
Zinc Porphyrins ◽  
Valuable Compounds ◽  
Imino Derivative

5,15-substituted porphyrins are valuable compounds in bioorganic and materials chemistry. A new synthesis has been developed that employs 1,9-diformylation of a dipyrromethane, conversion of the diformyldipyrromethane to the bis(imino) derivative, and reaction of the bis(imino)dipyrromethane + a dipyrromethane to give the zinc-porphyrin bearing trans-AB-substituents. 1,9-diformylation was achieved via Vilsmeier reaction. Imination was achieved by treatment of the 1,9-diformyldipyrromethane with excess amine under neat conditions at room temperature. The porphyrin-forming reaction was carried out over 2 h in refluxing ethanol containing zinc acetate exposed to air. Oxidation of the intermediate porphyrinogen occurs aerobically. A complex composed of two bis(imino)dipyrromethanes and two zinc atoms was observed to form reversibly during the course of the reaction. A set of zinc-porphyrins with trans-AB-, A 2-, or A-substituents has been prepared in yields of ~30% (without detectable scrambling) with straightforward purification. The reaction is applicable to A/B substituent combinations of aryl/aryl, aryl/alkyl, and aryl/H.

Synthesis of novel zinc porphyrins and their photocatalytic activity

2018 ◽  
Vol 47 (4) ◽  
pp. 360-366 ◽  
Author(s):  
Shao Rui Chen
Keyword(s):  
Photocatalytic Activity ◽  
Visible Light ◽  
Photoelectron Spectroscopy ◽  
Diffuse Reflectance Spectrum ◽  
X Ray Diffraction ◽  
Spacer Length ◽  
Content Type ◽  
Zinc Porphyrin ◽  
X Ray ◽  
Zinc Porphyrins

Purpose The purpose of this study is to investigate the effect of the spacer length of zinc porphyrin-TiO2 hybrids by photodegradation of methyl orange (MO) in aqueous solution under visible light. Design/methodology/approach 5-Mono-[4-hydroxyphenyl]-10,15,20-triphenylporphyrin was synthesized using Alder method. A new series of porphyrins and their corresponding zinc complexes (ZnPp) were obtained from 5-mono-[4-hydroxyphenyl]-10,15,20-triphenylporphyrin via nucleophilic substitution reaction. The ZnPp-TiO2 photocatalysts were prepared by loading ZnPp onto TiO2 and characterized by scanning electron microscope, X-ray diffraction, UV-vis diffuse reflectance spectrum and X-ray photoelectron spectroscopy. Findings The results indicated that zinc porphyrins were successfully loaded on the surface of TiO2 microsphere, which is crucial to enhance the activity of the catalytic composite under visible light. All the novel photocatalysts showed much enhanced photoactivity than bare TiO2. Among all the prepared ZnPp-TiO2, 5,10,15-triphenyl-20-[4-(4-naphthoxy)-butoxy]phenyl zinc porphyrin-TiO2 (4b) showed the highest photocatalytic activity for the degradation of MO. Research limitations/implications Synthesis of these zinc porphyrins had never been reported previously. Originality/value Four novel zinc porphyrin-TiO2 photocatalysts which could response to visible light in degradation of MO were synthesized using Alder method. The results show that the photocatalytic activity of 5,10,15-triphenyl-20-[4-(4-naphthoxy)butoxy] phenyl zinc porphyrin- TiO2 is higher than others.

Co-sensitization of free-base and zinc porphyrins: An effective approach to improve the photon-to-current conversion efficiency of dye-sensitized solar cells

2015 ◽  
Vol 19 (05) ◽  
pp. 695-707 ◽  
Author(s):  
Sandeep B. Mane ◽  
Liyang Luo ◽  
Hsin-Han Tsai ◽  
Chen-Hsiung Hung
Keyword(s):  
Solar Cells ◽  
Conversion Efficiency ◽  
Density Functional ◽  
Dye Sensitized Solar Cells ◽  
Visible Region ◽  
Free Base ◽  
Zinc Porphyrin ◽  
Dye Sensitized ◽  
Zinc Porphyrins ◽  
Sensitized Solar Cells

Co-sensitization of two or more sensitizers with complementary absorption profiles had been utilized as an imperative tool to achieve panchromatic sensitization in dye-sensitized solar cells. The highly efficient dye-sensitized solar cells consist of a co-sensitization system comprising of a mixture of porphyrin and organic dye. We have prepared four novel free-base and zinc porphyrins in minimum steps and examined their individual as well as co-sensitized performance in dye-sensitized solar cells. The UV-visible spectrum suggests that upon zinc insertion the absorption wavelength is red-shifted by 10 nm in both Soret and Q-band region. The density functional theory (DFT) calculations revealed that the presence of an electron withdrawing cyanoacrylic acid as the anchoring group has pronounced effect on the charge distribution. IPCE spectra suggest that the co-sensitization of a free-base porphyrin with a zinc porphyrin resulted in panchromatic absorption in whole visible region. The device made with Mix-2, which is composed from the free-base porphyrin N4CN and the zinc porphyrin N4ZnCN gave the best performance with an overall photon-to-current conversion efficiency of 4.18%, with Jsc of 10.4 mA.cm-2, Voc of 0.56 V and fill factor of 72%.

Kinetic Solvent Effects in Organic Reactions

2018 ◽  
Author(s):  
Belinda Slakman ◽  
Richard West
Keyword(s):  
Solvent Effect ◽  
Reaction Kinetics ◽  
Computational Methods ◽  
High Throughput ◽  
Kinetic Modeling ◽  
Solvent Effects ◽  
Reaction Rates ◽  
Prior Work ◽  
Solvent Phase ◽  
High Throughput Manner

<div> <div> <div> <p>This article reviews prior work studying reaction kinetics in solution, with the goal of using this information to improve detailed kinetic modeling in the solvent phase. Both experimental and computational methods for calculating reaction rates in liquids are reviewed. Previous studies, which used such methods to determine solvent effects, are then analyzed based on reaction family. Many of these studies correlate kinetic solvent effect with one or more solvent parameters or properties of reacting species, but it is not always possible, and investigations are usually done on too few reactions and solvents to truly generalize. From these studies, we present suggestions on how best to use data to generalize solvent effects for many different reaction types in a high throughput manner. </p> </div> </div> </div>

Fast self-exchange electron transfer and delocalization of unpaired electron between zinc porphyrin radical cations and zinc porphyrins

2003 ◽  
Vol 07 (05) ◽  
pp. 328-336 ◽  
Author(s):  
Shunichi Fukuzumi ◽  
Taku Hasobe ◽  
Yoshito Endo ◽  
Kei Ohkubo ◽  
Hiroshi Imahori
Keyword(s):  
Electron Transfer ◽  
Radical Cation ◽  
Unpaired Electron ◽  
Radical Cations ◽  
Esr Spectra ◽  
The Self ◽  
Fine Tuning ◽  
Transfer Rates ◽  
Zinc Porphyrin ◽  
Zinc Porphyrins

Self-exchange electron transfer rates between π-radical cations of zinc porphyrins and the neutral metalloporphyrins have been determined from the line-width broadening in the ESR spectra in different solvents at various temperatures. Fine tuning of the substituent on the porphyrin ring and the proper choice of the solvent have enabled us to observe negative activation enthalpies for the self-exchange electron transfer reactions. The observation of negative activation enthalpies indicates that the self-exchange electron transfer occurs via the charge-transfer π-complexes formed between zinc porphyrin radical cations and the neutral zinc porphyrins. The complete delocalization of the unpaired electron over two porphyrin moieties is observed in the radical cation of a zinc porphyrin dimer, 5,5'-bis(10,20-bis(3,5-di-tert-butylphenyl)porphyrinatozinc(II)). This is regarded as the extreme limit of the rapid self-exchange electron transfer between zinc porphyrin radical cation and the neutral form.

scholarly journals Determinants of the efficiency of photon upconversion by triplet–triplet annihilation in the solid state: zinc porphyrin derivatives in PVA

2017 ◽  
Vol 19 (34) ◽  
pp. 23471-23482 ◽  
Author(s):  
Ranjana Rautela ◽  
Neeraj K. Joshi ◽  
Sacha Novakovic ◽  
Wallace W. H. Wong ◽  
Jonathan M. White ◽  
...  
Keyword(s):  
Solid State ◽  
Zinc Porphyrin ◽  
Porphyrin Derivatives ◽  
Zinc Porphyrins ◽  
Triplet Triplet Annihilation

Differences in efficiencies of photon upconversion are explained for a series of alkyl-substituted diphenyl and tetraphenyl zinc porphyrins.

Kinetic Solvent Effects in Organic Reactions

2018 ◽  
Author(s):  
Belinda Slakman ◽  
Richard West
Keyword(s):  
Solvent Effect ◽  
Reaction Kinetics ◽  
Computational Methods ◽  
High Throughput ◽  
Kinetic Modeling ◽  
Solvent Effects ◽  
Reaction Rates ◽  
Prior Work ◽  
Solvent Phase ◽  
High Throughput Manner

<div> <div> <div> <p>This article reviews prior work studying reaction kinetics in solution, with the goal of using this information to improve detailed kinetic modeling in the solvent phase. Both experimental and computational methods for calculating reaction rates in liquids are reviewed. Previous studies, which used such methods to determine solvent effects, are then analyzed based on reaction family. Many of these studies correlate kinetic solvent effect with one or more solvent parameters or properties of reacting species, but it is not always possible, and investigations are usually done on too few reactions and solvents to truly generalize. From these studies, we present suggestions on how best to use data to generalize solvent effects for many different reaction types in a high throughput manner. </p> </div> </div> </div>

Sign in / Sign up

Export Citation Format

Share Document