A Rational Approach to Metal Loading of Organic Multi‐Site Polymers: Illusion or Reality?. Issue 21 (24th March 2018)

• Record Type: Journal Article
• Authors: Babel, Lucille; Baudet, Karine; Hoang, Thi Nhu Y.; Nozary, Homayoun; Piguet, Claude
• Is Part Of: Chemistry. Volume 24:Issue 21(2018)
• Page Start: 5423
• Page End: 5433
• Publication Date: 2018-03-24
• Subjects: host–guest systems -- lanthanideopolymers -- metallopolymers -- thermodynamics; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201705043
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Since its identification as an independent topic after the first world war, the chemistry of (bio)polymers and macromolecules rapidly benefited from intense synthetic activities driven by contributors focusing on formulation and structural aspects. Satisfying rationalization and predictions concerning polymer organization, stability, and reactivity were, however, delayed until the late fifties, when physical chemists set the basis of an adapted thermodynamic modeling. The recent emergence of metal‐containing (bio)organic polymers (i.e., metallopolymers) thus corresponds to a logical extension of this field with the ultimate goal of combining the rich magnetic and optical properties of open‐shell transition metals with the processability and structural variety of polymeric organic scaffolds. Since applications as energy storage materials, drug delivery vectors, shape‐memory materials, and photonic devices can be easily envisioned for these materials, the development of metallopolymers is faced with some urgency in producing novel exploitable structures, while the rational control of their formation, organization, and transformation remains elusive. Caught between the sometimes antagonistic requirements of economic efficiency on one side and of scientific pertinence on the other side, the ongoing achievements in the control of the metal loadings of multi‐site polymers are highlighted here with some tutorial discussions of luminescent lanthanidopolymers as proof‐of‐concept. Abstract : All the pertinent information concerning the metal loading of linear organic polymers can be obtained from the analysis of the experimental binding isotherms (orange traces) with the help of the site‐binding model. The resulting intrinsic affinities (grey arrows) and intersite interaction (blue arrow) provide a rational and instructed toolkit for programming metal organization and communication in metallopolymers.