scholarly journals Ring-fused porphyrins: extension of π-conjugation significantly affects the aromaticity and optical properties of the porphyrin π-systems and the Lewis acidity of the central metal ions

2015 ◽  
Vol 17 (22) ◽  
pp. 15001-15011 ◽  
Author(s):  
Yuta Saegusa ◽  
Tomoya Ishizuka ◽  
Keiyu Komamura ◽  
Soji Shimizu ◽  
Hiroaki Kotani ◽  
...  
Keyword(s):  
Optical Properties ◽  
Metal Ions ◽  
Lewis Acidity ◽  
Central Metal ◽  
Ring Fusion ◽  
Homo Lumo

The ring fusion with five-membered rings causes not only the narrowed HOMO–LUMO gaps but also the contribution of anti-aromatic resonance forms.

The effect of the cobalt and manganese central metal ions on the nonlinear optical properties of tetra(4-propargyloxyphenoxy)phthalocyanines

2018 ◽  
Vol 42 (12) ◽  
pp. 9857-9864 ◽  
Author(s):  
D. Mwanza ◽  
M. Louzada ◽  
J. Britton ◽  
E. Sekhosana ◽  
S. Khene ◽  
...  
Keyword(s):  
Optical Properties ◽  
Metal Ions ◽  
Excited States ◽  
Nonlinear Optical ◽  
Nonlinear Optical Properties ◽  
Central Metal ◽  
Optical Limiters ◽  
Paramagnetic Complexes

The phthalocyanines were investigated as optical limiters. The paramagnetic complexes were not effective owing to quenching of the excited states.

Molecular assemblies based on strong axial coordination in metal complexes of saddle-distorted dodecaphenylporphyrins

2015 ◽  
Vol 19 (01-03) ◽  
pp. 32-44 ◽  
Author(s):  
Tomoya Ishizuka ◽  
Shunichi Fukuzumi ◽  
Takahiko Kojima
Keyword(s):  
Electron Transfer ◽  
Metal Ions ◽  
Metal Complexes ◽  
Photoinduced Electron Transfer ◽  
Oxidation Potential ◽  
Metal Center ◽  
Lewis Acidity ◽  
Central Metal ◽  
Axial Coordination ◽  
Keggin Type

In this mini-review, we have highlighted our works on metal complexes having saddle-distorted dodecaphenylporphyrin (DPP) and its derivative as ligands in the light of enhancement of the Lewis acidity of a metal center coordinated by the porphyrin. The important point through this mini-review is ill-overlap of the out-of-plane lone pairs of pyrrole nitrogen atoms with σ-orbitals of the metal center bound to the saddle-distorted porphyrin core. The enhanced Lewis acidity of the central metal ions enabled us to construct stable molecular complexes through axial coordination using metal–DPP (M(DPP)) moieties ( M = Mo V or Sn IV ) and molecular or ionic entities with Lewis-basic coordination sites, including Keggin-type polyoxometallates (POM), which are known to have weak Lewis basicity and thus hard to coordinate to metal ions. A discrete 1:2 complex with a Ru -substituted POM performs catalytic substrate oxidation reactions in organic solvents. A 1:1 complex between Sn IV ( DPP ) and a Keggin-type POM exhibited photoinduced electron transfer, in which the Sn IV ( DPP ) moiety acts as an electron donor and the POM as an electron acceptor. Besides POM, other electron acceptors, including μ3-oxo trinuclear Ru III clusters and anthraquinone, having carboxyl groups as a linker unit also formed stable complexes with DPP-metal complexes as axial ligands to perform photoinduced electron transfer. Successful photoreactions of the M(DPP)-acceptor complexes are mainly enabled by the enhanced Lewis acidity of the DPP-metal complexes for the stabilization of the assemblies and also by lowering the oxidation potential of the porphyrin ligand to gain larger driving force of electron transfer to form an electron-transfer state with avoiding intersystem crossing. The stability and photochemical behavior are in sharp contrast to those for metal complexes with planar porphyrins as ligands.

Electrochemistry and spectroelectrochemistry of metallohexaphyrins containing bis-copper or bis-zinc central metal ions

2017 ◽  
Vol 21 (04-06) ◽  
pp. 311-321 ◽  
Author(s):  
Minyuan Chen ◽  
Zhongping Ou ◽  
Ru Feng ◽  
Yuanyuan Fang ◽  
Ying Zhang ◽  
...  
Keyword(s):  
Metal Ions ◽  
Pyrrole Ring ◽  
Central Metal ◽  
Tetrabutylammonium Perchlorate ◽  
Nonaqueous Media ◽  
Peak Separation ◽  
Scan Rate ◽  
Electron Transfers ◽  
Homo Lumo ◽  
Spectroelectrochemical Properties

Two meso-substituted bis-metallohexaphyrins were synthesized and characterized as to their electrochemical and spectroelectrochemical properties in nonaqueous media. The examined compounds are represented as HexaPyM2, where HexaPy represents an expanded macrocycle containing six pyrroles and M [Formula: see text] Cu(II) or Zn(II). Each hexaphyrin undergoes four reversible one-electron reductions and two irreversible oxidations in PhCN or CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate. The HexaPyCu2 is much easier to reduce than the corresponding Cu porphyrin with the same meso-substituents and it is also easier to reduce than a structurally related Cu(II) tripyrrinone. All four reductions of HexaPyM2 are assigned as [Formula: see text]-ring centered electron transfers to give [HexaPyM2][Formula: see text], [HexaPyM2][Formula: see text], [HexaPyM2][Formula: see text] and [HexaPyM2][Formula: see text], respectively. The neutral HexaPyCu2 and HexaPyZn2 also exhibit two oxidations, both of which are irreversible at a scan rate of 0.10 V/s. The peak separation between the first one-electron addition and the first electron abstraction of HexaPyM2 ranges from 1.46 to 1.72 V. These non-thermodynamic HOMO–LUMO gaps are similar to the range of HOMO–LUMO gaps for previously characterized sapphyrins which contain five pyrrole ring in the macrocycle.

scholarly journals Steady state charge conduction through solution processed liquid crystalline lanthanide bisphthalocyanine films

2019 ◽  
Vol 23 (11n12) ◽  
pp. 1603-1615
Author(s):  
Chandana Pal ◽  
Isabelle Chambrier ◽  
Andrew N. Cammidge ◽  
A. K. Sharma ◽  
Asim K. Ray
Keyword(s):  
Metal Ions ◽  
Liquid Crystalline ◽  
Microscopy Study ◽  
Individual Characteristics ◽  
Central Metal ◽  
Force Microscopy ◽  
Atomic Force ◽  
Double Decker ◽  
Order Of Magnitude ◽  
Chain Lengths

In-plane electrical characteristics of non-peripherally octyl(C[Formula: see text]H[Formula: see text]- and hexyl(C[Formula: see text]H[Formula: see text]-substituted liquid crystalline (LC) double decker lanthanide bisphthalocyanine (LnPc[Formula: see text] complexes with central metal ions lutetium (Lu), and gadolinium (Gd) have been measured in thin film formulations on interdigitated gold (Au) electrodes for the applied voltage ([Formula: see text] range of [Formula: see text]. The conduction mechanism is found to be Ohmic within the bias of [Formula: see text] while the bulk limited Poole–Frenkel mechanism is responsible for the higher bias. The compounds show individual characteristics depending on the central metal ions, substituent chain lengths and their mesophases. Values of 67.55 [Formula: see text]cm[Formula: see text] and 42.31 [Formula: see text]cm[Formula: see text] have been obtained for room temperature in-plane Ohmic conductivity of as-deposited octyl lutetium (C[Formula: see text]LuPc[Formula: see text] and hexyl gadolinium (C[Formula: see text]GdPc[Formula: see text] films, respectively while C[Formula: see text]GdPc[Formula: see text] films exhibit nearly two orders of magnitude smaller conductivity. On annealing at 80[Formula: see text]C, Ohmic conductivities of C[Formula: see text]LuPc[Formula: see text] and C[Formula: see text]GdPc[Formula: see text] are found to have increased but the conductivity of C[Formula: see text]GdPc[Formula: see text] decreased by more than one order of magnitude to 1.5 [Formula: see text]cm[Formula: see text]. For physical interpretation of the charge transport behavior of these three molecules, their UV-vis optical absorption spectra in the solution and in as-deposited and annealed solid phases and atomic force microscopy study have been performed. It is believed that both orientation and positional reorganizations are responsible, depending upon the size of the central ion and side chain length.

scholarly journals Utilization and simulation of innovative new binuclear Co(ii), Ni(ii), Cu(ii), and Zn(ii) diimine Schiff base complexes in sterilization and coronavirus resistance (Covid-19)

2021 ◽  
Vol 19 (1) ◽  
pp. 772-784
Author(s):  
Moamen S. Refat ◽  
Ahmed Gaber ◽  
Walaa F. Alsanie ◽  
Mohamed I. Kobeasy ◽  
Rozan Zakaria ◽  
...  
Keyword(s):  
Schiff Base ◽  
Molecular Docking ◽  
Metal Ions ◽  
Free Ligand ◽  
Schiff Base Complexes ◽  
Hydroxyl Groups ◽  
Binuclear Complexes ◽  
Central Metal ◽  
H Nmr ◽  
Biological Studies

Abstract This article aimed at the synthesis and molecular docking assessment of new diimine Schiff base ligand, namely 2-((E)-(2-((Z)-2-(4-chlorophenyl)-2-hydroxyvinyl)hydrazono) methyl)-6-methoxyphenol (methoxy-diim), via the condensation of 1-(4-chloro-phenyl)-2-hydrazino-ethenol compound with 2-((E)-(2-((Z)-2-(4-chlorophenyl)-2-hydroxy vinyl) hydrazono)methyl)-6-methoxyphenol in acetic acid as well as the preparation of new binuclear complexes of Co(ii), Ni(ii), Cu(ii), and Zn(ii). The following synthesized complexes were prepared in a ratio of 2:1 (metal/ligand). The 1H-NMR, UV-Vis, and FTIR spectroscopic data; molar conductivity measurements; and microanalytical, XRD, TGA/DTG, and biological studies were carried out to determine the molecular structure of these complexes. According to the spectroscopic analysis, the two central metal ions were coordinated with the diamine ligand via the nitrogen of the hydrazine and oxygen of the hydroxyl groups for the first metal ions and via the nitrogen of the hydrazine and oxygen of the phenol group for the second metal ions. Molecular docking for the free ligand was carried out against the breast cancer 3hb5-oxidoreductase and the 4o1v-protein binding kidney cancer and COVID-19 protease, and good results were obtained.

MetLigDB: a web-based database for the identification of chemical groups to design metalloprotein inhibitors

2011 ◽  
Vol 44 (4) ◽  
pp. 878-881 ◽  
Author(s):  
Hwanho Choi ◽  
Hongsuk Kang ◽  
Hwangseo Park
Keyword(s):  
Drug Discovery ◽  
Metal Ions ◽  
Metal Ion ◽  
Central Metal ◽  
Amino Acid Residues ◽  
Web Based ◽  
Additional Information ◽  
Chemical Groups ◽  
Insight Into ◽  
Chelating Groups

MetLigDB (http://silver.sejong.ac.kr/MetLigDB) is a publicly accessible web-based database through which the interactions between a variety of chelating groups and various central metal ions in the active site of metalloproteins can be explored in detail. Additional information can also be retrieved, including protein and inhibitor names, the amino acid residues coordinated to the central metal ion, and the binding affinity of the inhibitor for the target metalloprotein. Although many metalloproteins have been considered promising targets for drug discovery, it is difficult to discover new inhibitors because of the difficulty in designing a suitable chelating moiety to impair the catalytic activity of the central metal ion. Because both common and specific chelating groups can be identified for varying metal ions and the associated coordination environments, MetLigDB is expected to give users insight into designing new inhibitors of metalloproteins for drug discovery.

Understanding the sensing mechanisms of perovskite materials for gases with different properties, a perspective from the oxidation-reduction states of the central metal ions

2021 ◽  
Author(s):  
Bing Zhang ◽  
Yang Yang ◽  
Lei Tong ◽  
Xiaogang Wang ◽  
Bin Hu ◽  
...  
Keyword(s):  
Metal Ions ◽  
Gas Sensing ◽  
Structural Instability ◽  
Central Metal ◽  
Perovskite Materials ◽  
Oxidation Reduction

The structural instability and vague sensing mechanisms of perovskite materials when detecting gases with different properties are two main obstacles to the development of novel perovskite gas-sensing materials with high...

Microporous lanthanide metal-organic frameworks

2012 ◽  
Vol 32 (2-4) ◽  
pp. 81-100 ◽  
Author(s):  
Yao Chen ◽  
Shengqian Ma
Keyword(s):  
Optical Properties ◽  
Metal Ions ◽  
Porous Materials ◽  
Chemical Sensing ◽  
Metal Organic Frameworks ◽  
Current Status ◽  
Multifunctional Materials ◽  
Metal Organic ◽  
Lanthanide Metal ◽  
Solvent Adsorption

AbstractMicroporous metal-organic frameworks (MOFs) based on lanthanide metal ions or clusters represent a group of porous materials, featuring interesting coordination, electronic, and optical properties. These attractive properties in combination with the porosity make microporous lanthanide MOFs (Ln-MOFs) hold the promise for various applications. This review is to provide an overview of the current status of the research in microporous Ln-MOFs, and highlight their potential as types of multifunctional materials for applications in gas/solvent adsorption and separation, luminescence and chemical sensing and catalysis.

scholarly journals Structural, Spectroscopic and Optical Properties of Monohydrated Adenine: A Theoretical Study

2016 ◽  
Vol 64 (2) ◽  
pp. 157-161
Author(s):  
M Alauddin ◽  
MM Islam ◽  
MA Aziz
Keyword(s):  
Optical Properties ◽  
Band Gap ◽  
Theoretical Study ◽  
Minimum Energy ◽  
Band Gap Energy ◽  
Gap Energy ◽  
B3lyp Level ◽  
A Minor ◽  
Homo Lumo ◽  
Hydrogen Bonded

The structural, spectroscopic (IR, NMR and UV-Vis), electronic and optical properties of monohydrated adenine (monohydrated 6-aminopurine, C5H5N5.H2O) are investigated theoretically using DFT/B3LYP level of theory. Three minimum energy structures have been identified for monohydrated of adenine where H2O molecule is doubly hydrogen bonded with adenine.1H NMR analysis shows that the protons which are hydrogen bonded become deshielded and chemical shift moves to the higher frequency region.Five IR active mode of vibrations were found at 3108, 3295, 3665, 3676 and 3719 cm-1 which are assigned as bonded -OH vibration of H2O, Bonded -NH vibration of NH2, Free -NH vibration of adenine (9 N), Free -NH vibration of NH2, Free -OH vibration of H2O, respectively and agree well with the available experimental results. The investigation of electronic properties shows that the HOMO-LUMO band gap energy of monohydrated adenine at B3LYP level is 5.15 eV. The major electronic transition (from HOMO to LUMO (83%) (π→π*)) occurs at 258 nm (4.80 eV) with a minor transition at 237 nm (5.23 eV). Theoretically it is observed that the HOMO-LUMO band gap energy is for monohydrated adenine is lower than that of adenine. Dhaka Univ. J. Sci. 64(2): 157-161, 2016 (July)

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