Synthesis and Properties of Polyimide with Diazacrown Ether Moiety and the Corresponding Polymer Barium Complexes

Abstract

A series of polyimides with diaza-18-crown-6 moieties on the main chain were synthesized by the reaction between 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and different macrocyclic diamine monomers. The polyimide barium complexes were also synthesized from the corresponding monomeric barium complexes. An X-ray crystal structure of one of the monomers was also determined. Good quality, free-standing polymer films were obtained by thermal imidization of the poly(amic acid) presursors. No decomposition of the barium complexes was found during the thermal imidization processes. The polyimides and their barium complexes exhibit different electronic absorption properties, which is attributed to the formation of charge-transfer excited states. The binding of barium ion to the polymer main chain may affect the energy level of the resulting charge transfer states. In addition, the emission properties of the polyimides with and without barium ion are also different. Changes in the emission spectrum were observed when the metal-free polyimide film was immersed in barium solution. These materials may serve as potential candidates as sensors for barium or other alkaline earth metals.

Polymer Possessing Diaza-18-crown 6-Ether Linked by π-Conjugated Aminopenta-2,4-dienylidene Groups Generated by Ring-opening of Pyridinium Ring

“…For example, polymers containing the diazacrown ether linked by amide groups or imide groups show unique optical and electrochemical properties on the basis of functionalities of the linkers. 5,6 To the best of our knowledge, there is no report on main chain polymers possessing the diazacrown ether linked by -conjugated chains. Such a polymer will show interesting chemical properties upon complexation of the diazacrown ether with metal ions since the -conjugated system may expand through the metal complex of the diazacrown ether.…”

“…Their structures were determined by 1 H and 13 C NMR spectroscopy. Figure 1 depicts 1 H NMR spectra of polymer-1 and model-1 in DMSO-d 6 . As seen in Figure 1, peaks due to hydrogen atoms H a , H b , and H c of polymer-1 and model-1 appear at approximately 7.8, 7.4, and 5.9 in a 2:1:2 integral ratio, respectively.…”

One-Pot Reaction Involving Two Different Amines and Formaldehyde Leading to the Formation of Poly(Macrocyclic) Cu(II) Complexes

“…[1][2][3][4][5][6][7][8][9][10][11][12] Most polymer complexes are known to be insoluble in water, though watersoluble macromolecules or polymers are of importance for many industrial and technological applications.…”

“…[8][9][10][11][12] The preparation of such compounds generally starts with a pre-formed polyaza macrocycle that can react with polymer bearing reactive functional groups or with α,ω-difunctionalized reagents. For instance, the unsaturated poly(tetraaza macrocycle) A (Scheme 1) has been prepared by the reaction of L 1 with the diisocyanate OCN-(CH 2 ) 6 -NCO.…”

Syntheses, spectroscopic characterization and metal ion binding properties of benzo-15-crown-5 derivatives and their sodium and nickel(II) complexes

“…Since the pioneering publication of Pedersen in 1967 extensive research has been devoted to the preparation and study of the properties of macrocyclic polyethers [1][2][3][4].…”