Iminophosphorano‐Substituted Bispyridinylidenes: Redox Potentials and Substituent Constants from Tolman Electronic Parameters

2020 ◽  
Vol 26 (72) ◽  
pp. 17371-17375
Author(s):  
Nicholas A. Richard ◽  
Chun Keat Khor ◽  
Sydney M. Hetherington ◽  
Scott L. Mills ◽  
Andreas Decken ◽  
...  
Keyword(s):  
Redox Potentials ◽  
Electronic Parameters ◽  
Substituent Constants

Solvent and substituent effects on UV-vis spectra and redox properties of zinc p-hydroxylphenylporphyrins

2017 ◽  
Vol 21 (07n08) ◽  
pp. 465-475 ◽  
Author(s):  
Guifen Lu ◽  
Xiaoqin Jiang ◽  
Zhongping Ou ◽  
Sen Yan ◽  
Karl M. Kadish
Keyword(s):  
Substituent Effects ◽  
Phenyl Group ◽  
Nonaqueous Solvents ◽  
Donor Number ◽  
Redox Potentials ◽  
The Third ◽  
Visible Spectra ◽  
Phenyl Rings ◽  
Substituent Constants ◽  
Uv Visible

A series of zinc[Formula: see text]-hydroxylphenylporphyrins was synthesized and characterized by spectroscopic and electrochemical methods in four different nonaqueous solvents. The investigated compounds are represented as [([Formula: see text]-HOPh)[Formula: see text](ptBuPh)[Formula: see text]P]Zn, where P represents the dianion of a porphyrin, Ph represents a phenyl group, HO and [Formula: see text]Bu are para substituents on the meso-phenyl rings of the macrocycle and [Formula: see text] = 0–4. The four utilized nonaqueous solvents were dichloromethane (CH[Formula: see text]Cl[Formula: see text], NN-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and pyridine (Py) which were selected on the basis of their coordinating capabilities. The UV-visible spectra and redox potentials of each porphyrin were analyzed both as a function of Hammett substituent constants for groups at the para-positions of the meso-phenyl rings and as a function of the Gutmann solvent donor number which is related to the coordinating ability of the solvent. Each porphyrin exhibits two reductions in CH[Formula: see text]Cl[Formula: see text], DMSO and Py while three reductions are observed in DMF, the additional reaction being due to a phlorin product generated in solution after formation of the porphyrin dianion. Two or three reversible oxidations were seen in CH[Formula: see text]Cl[Formula: see text], the exact number depending upon the specific porphyrin and the presence of [Formula: see text]-OH substituents at the meso-phenyl rings of the compound. The first two oxidations were assigned as involving the conjugated macrocycle and the third is associated with oxidation of the meso-HOPh group(s).

The Phthalocyanines — Molecules of Enduring Value; a Two-dimensional Analysis of Redox Potentials

1999 ◽  
Vol 03 (06) ◽  
pp. 488-499 ◽  
Author(s):  
A. B. P. LEVER
Keyword(s):  
Electrochemical Properties ◽  
Preliminary Test ◽  
Two Dimensional ◽  
Redox Potentials ◽  
Dimensional Approach ◽  
Sensor Applications ◽  
Electrochemical Parameters ◽  
Substituent Constants ◽  
Design Requirements ◽  
Hammett Parameters

The sensor applications of MPc derivatives on carbon-type electrodes are briefly reviewed. The electrochemical properties of metallophthalocyanines in solution and on a surface are reviewed with emphasis on predicting redox potentials using Hammett substituent constants and using ligand electrochemical parameters. Design requirements for a two-electron redox process at a metallophthalocyanine center are discussed. A two-dimensional approach using both Hammett parameters and ligand electrochemical parameters is introduced. Some preliminary test examples are presented.

The relationship between redox potentials and substituent constants in biologically active arylazoxy compounds

2005 ◽  
Vol 579 (1) ◽  
pp. 33-41 ◽  
Author(s):  
Francine Santos de Paula ◽  
Écio Matias Sales ◽  
Maura Vallaro ◽  
Roberta Fruttero ◽  
Marília O.F. Goulart
Keyword(s):  
Biologically Active ◽  
Redox Potentials ◽  
Substituent Constants ◽  
The Relationship

Using A Segmented Voltage Sweep Mode and A Gaussian Curve Fitting Method to Improve Heavy Metal Measurement System Performance

2012 ◽  
Vol 19 (2) ◽  
pp. 381-394
Author(s):  
José Pereira ◽  
Octavian Postolache ◽  
Pedro Girão
Keyword(s):  
Heavy Metals ◽  
Heavy Metal ◽  
Measurement System ◽  
Curve Fitting ◽  
System Performance ◽  
Redox Potentials ◽  
Voltage Sweep ◽  
Gaussian Curve ◽  
Fitting Method ◽  
Curve Fitting Method

Using A Segmented Voltage Sweep Mode and A Gaussian Curve Fitting Method to Improve Heavy Metal Measurement System PerformanceThis paper presents a voltammetric segmented voltage sweep mode that can be used to identify and measure heavy metals' concentrations. The proposed sweep mode covers a set of voltage ranges that are centered around the redox potentials of the metals that are under analysis. The heavy metal measurement system can take advantage of the historical database of measurements to identify the metals with higher concentrations in a given geographical area, and perform a segmented sweep around predefined voltage ranges or, alternatively, the system can perform a fast linear voltage sweep to identify the voltammetric current peaks and then perform a segmented voltage sweep around the set of voltages that are associated with the voltammetric current peaks. The paper also includes the presentation of two auto-calibration modes that can be used to improve system's reliability and proposes the usage of a Gaussian curve fitting of voltammetric data to identify heavy metals and to evaluate their concentrations. Several simulation and experimental results, that validate the theoretical expectations, are also presented in the paper.

1,1’-Biaceanthrylene and 2,2'-Biaceanthrylene: Models for Linking Larger Polycyclic Aromatic Hydrocarbons via Five-Membered Rings

2019 ◽  
Author(s):  
Yachu Du ◽  
Kyle Plunkett
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Polycyclic Aromatic Hydrocarbon ◽  
Aromatic Hydrocarbon ◽  
Electronic Properties ◽  
Aromatic Hydrocarbons ◽  
Model Systems ◽  
Redox Potentials ◽  
Dimer Model ◽  
Optical And Electronic Properties ◽  
Polycyclic Aromatic

We show that polycyclic aromatic hydrocarbon (PAH) chromophores that are linked between two five-membered rings can access planarized structures with reduced optical gaps and redox potentials. Two aceanthrylene chromophores were connected into dimer model systems with the chromophores either projected outward (2,2’-biaceanthrylene) or inward (1,1’-biaceanthrylene) and the optical and electronic properties were compared. Only the planar 2,2’-biaceanthrylene system showed significant reductions of the optical gaps (1 eV) and redox potentials in relation to the aceanthrylene monomer.<br>

1,1’-Biaceanthrylene and 2,2'-Biaceanthrylene: Models for Linking Larger Polycyclic Aromatic Hydrocarbons via Five-Membered Rings

2019 ◽  
Author(s):  
Yachu Du ◽  
Kyle Plunkett
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Polycyclic Aromatic Hydrocarbon ◽  
Aromatic Hydrocarbon ◽  
Electronic Properties ◽  
Aromatic Hydrocarbons ◽  
Model Systems ◽  
Redox Potentials ◽  
Dimer Model ◽  
Optical And Electronic Properties ◽  
Polycyclic Aromatic

We show that polycyclic aromatic hydrocarbon (PAH) chromophores that are linked between two five-membered rings can access planarized structures with reduced optical gaps and redox potentials. Two aceanthrylene chromophores were connected into dimer model systems with the chromophores either projected outward (2,2’-biaceanthrylene) or inward (1,1’-biaceanthrylene) and the optical and electronic properties were compared. Only the planar 2,2’-biaceanthrylene system showed significant reductions of the optical gaps (1 eV) and redox potentials in relation to the aceanthrylene monomer.<br>

Transjøen, a Groundwater Influenced Lake with Special Redox and Sulphate Conditions

1976 ◽  
Vol 7 (5) ◽  
pp. 307-320 ◽  
Author(s):  
G. S. Bremmeng ◽  
A. E. Kloster
Keyword(s):  
Calcium Carbonate ◽  
Chemical Composition ◽  
Lower Layer ◽  
Calcium Content ◽  
Meromictic Lake ◽  
Redox Potentials ◽  
Precipitated Calcium Carbonate

Transjøen, a lake in S.E. Norway investigated hydrographically from October 1969 to October 1971, consists of two basins, both of which are meromictic (lake with lower layer which does not participate in the periodic circulations). The lake has a large influx of groundwater of very varying chemical composition. The calcium content is high and precipitated calcium carbonate and electrolyte rich groundwater is assumed to be the main reason for the meromictic stability. The redox potentials of monimolimnion (the lower layer which does not participtate in the periodic circulation) are extremely low, but in spite of this fact the content of sulphate is high.

Substituent effects in 1,3-indanediones

1982 ◽  
Vol 47 (5) ◽  
pp. 1486-1493 ◽  
Author(s):  
Alexander Perjéssy
Keyword(s):  
Substituent Effects ◽  
Empirical Equations ◽  
Substituent Constants ◽  
Complex Structural

The carbonyl stretching frequencies correlate well with substituent constants in a series of 166 1,3-indanediones using improved and extended Seth-Paul-Van Duyse equation. Transmissive factors and group electronegativities have been used to find empirical equations for calculation of substituent constants of more complex structural fragments.

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