2,6-Diacetylpyridine and 1,2-diaminoethane in the presence of copper(II) and zinc(II) chlorides containing a few drops of acetic acid were condensed into compositions [CuLH2]2.2HCl.H2O (1), [Cu2LPyz]2.2HCl.4CH3COCH3 (2) [CuZnLPyz]2.2HCl.2CH3COCH3.10H2O (3) and [ZnL'Cl]3.3HCl.3H2O (4) substantiated by elemental analyses, IR, UV-vis, 1H NMR and FAB mass spectral data. Demetallation of a Ni(II) complex (isolated as above) afforded macrocyclic skeleton LH4, whereas L' symbolizes a skeleton of the ligand containing only ethylenediamine and 2,6-diacetylpyridine. Molecular structure optimization using MM2 force field calculations for the complexes revealed distorted square pyramidal geometry around Cu(II) centers in complexes 1 and 2 and tetrahedral geometry around Cu(II) and Zn(II) centers with different degrees of distortion in complex 3 whereas three Zn(II) atoms (each in distorted square pyramidal geometry) attached via Cl bridges form a cyclic structure in complex 4. In complexes 1 and 2,Cu-Cu = 2.63-2.66 angstroms indicated the possibility of coupling between the two Cu(II) centers which has been supported by lower magnetic moment as well as ESR spectra showing half-field signal.

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.saa.2004.06.017DOI Listing

Publication Analysis

Top Keywords

macrocyclic skeleton
8
molecular structure
8
structure optimization
8
distorted square
8
square pyramidal
8
pyramidal geometry
8
geometry cuii
8
cuii centers
8
pentacoordinated cuii/znii
4
complexes
4

Similar Publications

Fluorescent Macrocyclic Arenes: Synthesis and Applications.

Angew Chem Int Ed Engl

January 2025

Institute of Chemistry Chinese Academy of Sciences, CAS Key Laboratory of Molecular Recognition and Function, Zhongguancun North First Street 2, 100190, Beijing, CHINA.

Fluorescent macrocyclic arenes have attracted increasing interest in macrocyclic and supramolecular chemistry due to their exceptional photophysical properties and versatile applications. Classical macrocyclic arenes modified with fluorescent groups at the upper or bottom rims have long provided valuable platforms across various fields. Recently, a large number of novel fluorescent macrocyclic arenes directly composed of polycyclic aromatic or heteroaromatic building blocks including naphthalene, anthracene, tetraphenylethene, pyrene, fluorene, carbazole, acridan, phenothiazine, coumarin,  triphenylamine, benzothiadiazole and so on, have been reported, and they have shown specific fluorescent property, and also exhibited broad applications in molecular recognition, sensing, bioimaging and functional materials.

View Article and Find Full Text PDF

From Monocyclization to Pentacyclization: A Versatile Plant Cyclase Produces Diverse Sesterterpenes with Anti-Liver Fibrosis Potential.

Adv Sci (Weinh)

January 2025

State Key Laboratory of Southwestern Chinese Medicine Resources, and Innovative Institute of Chinese Medicine and Pharmacy, Chengdu University of Traditional Chinese Medicine, Chengdu, 611137, P. R. China.

A prolific multi-product sesterterpene synthase CbTPS1 is characterized from the medicinal Brassicaceae plant Capsella bursa-pastoris. Twenty different sesterterpenes including 16 undescribed compounds, possessing 10 different mono-/di-/tri-/tetra-/penta-carbocyclic skeletons, including the unique 15-membered macrocyclic and 24(15→14)-abeo-capbuane scaffolds, are isolated and structurally elucidated from engineered Escherichia coli strains expressing CbTPS1. Site-directed mutagenesis assisted by molecular dynamics simulations resulted in the variant L354M with up to 13.

View Article and Find Full Text PDF

Nidustrin A, cysteine-retained emestrin with a unique 18-membered macrocyclic lactone from the endophytic fungus Aspergillus nidulans.

Bioorg Chem

December 2024

Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, PR China. Electronic address:

Nidustrin A (1), the first cysteine-retained emestrin featuring a unique sulfur-containing 18-membered macrocyclic lactone, along with four biogenetically related compounds (2-5), and one known analogue secoemestrin C (6), were isolated from the large-scale culture of Aspergillus nidulans, an endophytic fungus derived from the Whitmania pigra. Compounds 2 and 3 represent the second examples of noremestrin besides the previously reported noremestrin A, and the single crystal X-ray diffraction analysis of compound 2 provided solid evidence for the intriguing skeleton of noremestrin. Their structures were determined by extensive spectroscopic data, electronic circular dichroism calculations, and single-crystal X-ray diffraction.

View Article and Find Full Text PDF

Macrocyclic Compounds with Diverse Skeletons from the Roots of and Their Spasmolytic Activity.

J Nat Prod

December 2024

Key Laboratory of Chemistry in Ethnic Medicinal Resources, Ministry of Education of China, School of Ethnomedicine and Ethnopharmacy, Yunnan Minzu University, Kunming 650504, People's Republic of China.

Six undescribed macrocyclic compounds, including diarylhexanoids ( and ), a diarylhexanoid glucoside (), diarylheptanoids ( and ), and an aceroside (), were isolated from the roots of Cheval., along with 11 known analogues (-). The structures were elucidated by spectroscopic analysis, as well as by calculated optical rotatory dispersion and derivatization reactions.

View Article and Find Full Text PDF

Total Synthesis of Exiguolide Stereoisomers: Impact of Stereochemical Permutation on Reactivity, Conformation, and Biological Activity.

J Org Chem

January 2025

Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan.

(-)-Exiguolide is a marine macrolide natural product with potent anticancer activity. In this study, the total synthesis of exiguolide stereoisomers, (9)-exiguolide, (9,13)-exiguolide, and (9,13,19)-exiguolide, was achieved by capitalizing on our macrocyclization/transannular pyran cyclization strategy. The impact of the stereochemical permutation on the reactivity of advanced intermediates, the conformation of the macrocyclic skeleton, and the antiproliferative activity against human cancer cells were investigated in detail.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!