Investigating reaction conditions for controlling the self-assembly of metal-seamed pyrogallol[4]arene nanocapsules

2019 ◽  
Author(s):  
◽  
Asanka Sajeewani Rathnayake
Keyword(s):  
Metal Ions ◽  
Self Assembly ◽  
Mixed Valence ◽  
Transition Metal Ions ◽  
Ambient Conditions ◽  
Reaction Conditions ◽  
University Of Missouri ◽  
Reduction Reactions ◽  
Oxidation Reduction ◽  
The University

[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT REQUEST OF AUTHOR.] Upon coordination to metal ions, C-alkylpyrogallol[4]arenes (PgCn, where n is the number of carbon atoms in the pendant alkyl chains), can be assembled into spherical metal-organic nanocapsules (MONCs). MONCs are generally arranged into two different structural types, hexamers and dimers, of which six or two PgCn units assemble into capsular structures by coordination to 24 or 8 metal ions, respectively. Co[II]-, Zn[II]-, and Mn[II]-coordinated MONCs have been synthesized under ambient conditions and structurally characterized. Under certain reaction conditions, some transition metal ions and other reagents seem to act as electron accepting or donating reagents, such that appropriate oxidation or reduction reactions may occur. These types of in-situ redox reactions lead to the formation of mixed-valence Mn[II]/Mn[III]- and Fe[II]/Fe[III]-seamed MONCs. The occurrence of such oxidation/reduction reactions appears to be promoted by certain factors such as resulting pH conditions, size of the coordinating ions/ligands, and oxidizing/reducing abilities of reagents used in each synthesis. In addition, studies have been carried out to incorporate some defects into the MONC outer framework by using mixed-macrocycles as the starting materials. Mixed-macrocycles are synthesized by fusing both resorcinol and pyrogallol into the same macrocycle, and the position of resorcinol units in the MONC usually appears as a hole or defect on the capsule surface. Incorporations of such defects give MONCs potential for, for example, selective filtering of small molecules into the capsule interior and magnetic and electronic applications by varying the electrostatic interaction between adjacent metal ions.

Self assembly of a tren-derivative hydrogenated Schiff base with transition metal ions: syntheses, crystal structures and photoluminescent properties

CrystEngComm ◽  
2012 ◽  
Vol 14 (8) ◽  
pp. 2879 ◽  
Author(s):  
Yuehong Wen ◽  
Tianlu Sheng ◽  
Qilong Zhu ◽  
Shengmin Hu ◽  
Chunhong Tan ◽  
...  
Keyword(s):  
Schiff Base ◽  
Transition Metal ◽  
Metal Ions ◽  
Crystal Structures ◽  
Self Assembly ◽  
Transition Metal Ions

scholarly journals Supramolecular complexes of cobalt(II), manganese(II) and cadmium(II) with bis(terpyridine) ligand as novel luminescent materials

2013 ◽  
Vol 15 (3) ◽  
pp. 91-95 ◽  
Author(s):  
Monika Wałęsa-Chorab ◽  
Adam Gorczyński ◽  
Damian Marcinkowski ◽  
Zbigniew Hnatejko ◽  
Violetta Patroniak
Keyword(s):  
Transition Metal ◽  
Metal Ions ◽  
Electronic Absorption ◽  
Self Assembly ◽  
Emission Spectra ◽  
Transition Metal Ions ◽  
Supramolecular Complexes ◽  
Luminescent Materials ◽  
Absorption And Emission ◽  
Counter Ions

Abstract Self-assembly of N6-donor bis(terpyridine) ligand L with transition metal ions: Co(II), Mn(II) and Cd(II) leads to a formation of three kinds of supramolecular complexes. In the electronic absorption and emission spectra of supramolecular complexes additional bands were observed what was ascribed to the coordination of ligand molecules to metal ions. Luminescence properties of these complexes strongly depend on the kind of metal ions and counter ions. The effective blue luminescence was observed in the case of Mn(II) and Cd(II) complexes in which all N-donor atoms of ligand molecules coordinate with the metal center

scholarly journals Metallo-Supramolecular Hydrogels from the Copolymers of Acrylic Acid and 4-(2,2′:6′,2″-terpyridin-4′-yl)styrene

Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1152 ◽  
Author(s):  
Huiqin Zhang ◽  
Pan Liu ◽  
Zheng Chi ◽  
Xuegang Chen
Keyword(s):  
Transition Metal ◽  
Acrylic Acid ◽  
Metal Ions ◽  
Self Assembly ◽  
Wavelength Region ◽  
Transition Metal Ions ◽  
Ion Concentration ◽  
Iron Ions ◽  
Absorption Intensity ◽  
Dilute Aqueous Solution

Hydrophilic copolymers containing 2,2′:6′,2″-terpyridine moieties and acrylic acid (AA) units poly (acrylic acid-co-4-(2,2′:6′,2″-terpyridin-4′-yl)styrene) (P(AA-co-TPY)) were synthesized and characterized. Coordinated with different transition metal ions, the dilute aqueous solution of the copolymers exhibited red-shifted UV-vis absorption peaks of π-π* transition from 317 to 340 nm. Further, interacting with iron ions, the copolymer showed new absorption peaks at a longer wavelength region (570 nm) and the absorption intensity enhanced with increase of the ion concentration. When enough ions were added to coordinate with the 2,2′:6′,2″-terpyridine moieties, novel metallo-supramolecular hydrogels were obtained due to the formation of metal coordination bonds between polymer back bones and transition metal ions (Ni2+, Zn2+, Cd2+, Fe2+ and Cu2+), which acted as self-assembly crosslinking structures. The mechanical strength and morphology of the resulting metallo-supramolecular hydrogels have been investigated.

Design and gas sorption study of c-alkylresorcin[n]arene-based cocrystals

2017 ◽  
Author(s):  
◽  
Shan Jiang
Keyword(s):  
Self Assembly ◽  
Guest Molecule ◽  
The Novel ◽  
Gas Sorption ◽  
X Ray Diffraction ◽  
University Of Missouri ◽  
X Ray ◽  
Solvent Systems ◽  
The University ◽  
Sorption Study

[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT AUTHOR'S REQUEST.] Supramolecular chemistry is the study of how to form complexes through molecular self-assembly and intermolecular bonding. Our research group has been doing a lot supramolecular research based on macrocycles such as calixarenes, pyrogallolarenes and resorcinarens. This research is interested in formation of novel C-alkyresorcin[n]arene( n=4,6) based cocrystals. The basic plan is to design and synthesize cocrystals, then analyze the crystal structure via single crystal X-ray diffraction technique, and determine if the novel cocrystal has the ability to absorb gases such as carbon dioxide and nitrogen. Chapter two is about the cocrystallization of six different C-alkylresorcin[4]arene according the chain length and guest molecule 1-(2-pyridylazo)-2-naphthol( PAN) in four solvent systems. Five successfully synthesized cocrystals' structure and synthesis are discussed. Chapter three talks how to use cocrystallization as a separation method to separate C-ethylresocin[6]arene from C-ethylresorcin[4]arene. Three noval C-ethylresorcin[6]arene based cocrystals from three different solvents are discussed. Chapter four investigates the cocrystallization between C-ethylresorcin[n]arene (n=4, 6) with 4, 4'-bipyridine. It discusses how solvent and component concentration affect such cocrystallization. Chapter five uses cocrystal formed from C-ethylresorcin[6]arene and 1,2-bis(4-pyridyl)ethane in acetone as the gas sorption candidate to test its ability to absorb gases after solvent removal. The conditions of removing solvents and gas sorption results are discussed.

Supramolecular arrays by the self-assembly of terpyridine-based monomers with transition metal ions

2018 ◽  
Vol 47 (22) ◽  
pp. 7528-7533 ◽  
Author(s):  
Ting-Zheng Xie ◽  
Yuchen Yao ◽  
Xinyu Sun ◽  
Kevin J. Endres ◽  
Shiying Zhu ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Ions ◽  
Self Assembly ◽  
Weak Interactions ◽  
Building Blocks ◽  
Transition Metal Ions ◽  
The Self

Hierarchical construction of a highly ordered supramolecular array has been, in general, a challenge due to the complexation of building blocks and the hard-to-control weak interactions.

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