Characterization of Defined Metal‐Containing Supramolecular Block Copolymers

Abstract

The characterization of metal‐containing supramolecular polymers by gel permeation chromatography (GPC) or matrix‐assisted laser desorption ionisation time‐of‐flight mass spectrometry (MALDI‐TOF MS) is complicated because of the interaction of the charged materials with the GPC column material in the first case and fragmentation due to the applied laser energy in the latter case. In this contribution we report recent advances made for the characterization of supramolecular polymers based on terpyridine metal complexes utilizing GPC and MALDI‐TOF MS. In particular for GPC analysis, the choice of solvent and additive was found to be crucial for a successful characterization. Furthermore, MALDI‐TOF MS spectra of these compounds are not straightforward to interpret. Both aspects are discussed in detail with the result of a better understanding and improved analysis possibilities of the mentioned supramolecular polymers.

Water‐Soluble Building Blocks for Terpyridine‐Containing Supramolecular Polymers: Synthesis, Complexation, and pH Stability Studies of Poly(ethylene oxide) Moieties

“…We are currently trying to relate these observations to binding strengths and stabilities of these metal complexes and model systems. [13] The stability of the different metallo-supramolecular connecting units regarding pH variations was investigated in detail by varying the pH. First, the polymers were solubilized in different pH-buffers (pH ¼ 1.0, 3.0, 5.0, 7.0, 10.0, and 13.0) and investigated by UV/Vis spectroscopy.…”

“…The combined organic layers were dried over Na 2 SO 4 and removed in vacuo. The compounds were purified by preparative size exclusion chromatography (BioBeads SX-1, CH 2 Cl 2 ), followed by a double 13 C NMR (CDCl 3 ) (1-4): d ¼ 166.6 (C 4 0 ), 156.7 (C 2 0 , C 6 0 ), 155.6 (C 2 , C 2 00 ), 148.7 (C 6 , C 6 00 ), 136.4 (C 4 , C 4 00 ), 123.5 (C 5 , C 5 00 ), 120.9 (C 3 , C 3 00 ), 107.0 ( The terpyridine-functionalized poly(ethylene oxide) (0.250 g) and the metal salt M(OAc) 2 Â H 2 O (M ¼ Fe, Co, Ni, Cu, Zn, Cd; 0 < Â < 4) in a molar ratio of 2:1 were stirred under reflux in 10 mL of MeOH for at least 4 hours. The reaction was followed by UV/Vis: when no more changes were observed in the UV spectrum, NH 4 PF 6 (0.120 g, 0.73 mmol, 10-fold excess) was added to the solution.…”

Layer‐by‐Layer Deposition of Rhenium‐Containing Hyperbranched Polymers and Fabrication of Photovoltaic Cells

“…GPC analysis showed two peaks in the chromatogram, and the high-molecular-weight peak was attributed to the interaction between the charged polymer and the column materials. [33] We further studied the effect of salt on the polymer molecular size by static light scattering. In pure DMF solution, the radius of gyration r g of the polymer was measured as 23.5 nm.…”

Multifunctional Poly(N‐vinylcarbazole)‐Based Block Copolymers and their Nanofabrication and Photosensitizing Properties

“…[18] It has previously been shown that metal-containing polymers have a strong polymer-column and polymer-polymer interaction, which may give rise to overestimated molecular weights. [19] From the GPC chromatogram of polymer 4a ( Figure S1), it can be seen that the peak attributable to PVK initiator 1 disappears. However, two peaks are observed in the chromatogram.…”