Tetrazole functional copolymers: Facile access to well-defined Rhenium(I)-Polymeric luminescent materials

Well‐Defined Tetrazole‐Functional Copolymers as Macromolecular Ligands for Luminescent Ir(III) and Re(I) Metal Species: Synthesis, Photophysical Properties and Application in Bioimaging

“…SEC analysis indicated no impact on the molecular weight distribution of the endmodified PFPA homopolymer with the M n = 9200 and Ð = 1.08, Figure S2, Supporting Information. [22] Sequential reaction of the polyPFPA homopolymer with nbutylamine, BuNH 2 , and 5-aminotetrazole, TetNH 2 , yielded the target poly(n-butyl acrylamide-co-N-(1H-tetrazol-5-yl) acrylamide) statistical copolymer with a 55:45 molar composition. A similar n-butyl acrylamide-co-N-(1H-tetrazol-5-yl) acrylamide copolymer was also utilized that contained 24 mol% tetrazole repeat units and 76 mol% n-butyl acrylamide repeat units and was obtained from the same parent polyPFPA homopolymer.…”

“…Subsequently, complete desulfurization of the thiocarbonylthio end‐group was accomplished by reaction of the PFPA homopolymer with an excess of AIBN. [ 21,22,43,44 ] Successful end‐group removal was confirmed by UV–Vis spectroscopy as evidenced from the complete disappearance of the broad band covering ≈280–340 nm that is associated with the π ‐ π * transition of the C═S bond, Figure S1, Supporting Information. SEC analysis indicated no impact on the molecular weight distribution of the end‐modified PFPA homopolymer with the M n = 9200 and Ð = 1.08, Figure S2, Supporting Information.…”

“…The synthesis and characterization of the parent poly(n-butyl acrylamide-co-N-(1H-tetrazol-5-yl) acrylamide) materials were reported previously. [22] Dichlorotetrakis(2-(2-pyridinyl)phenyl)diiridium(III), [Ir 2 (ppy) 4 (𝜇-Cl 2 )], and [Ir(ppy) 2 (phenyltetrazolato) 2 ] (ppy = 2-phenyl-pyridine) were prepared according to the method of Fiorini et al [40] Re(CO) 3 (phen)Br was synthesized according to the method of Si et al [41] Synthesis of Iridium-Bound Functional Copolymers: Below was a typical procedure for the attachment of the [Ir(ppy) 2 ] + fragment to parent poly(nbutyl acrylamide-co-N-(1H-tetrazol-5-yl) acrylamide):…”

“…To address this issue, we subsequently reported a more facile approach to tetrazolefunctional materials via the post-polymerization modification of RAFT-prepared poly(pentafluorophenyl acrylate) with commercially available 5-aminotetrazole. [22] Exploiting the facile nucleophilic acyl substitution chemistry, especially with primary amines, associated with pentafluorophenyl esters, [14,[23][24][25][26][27] we described the synthesis of a small library of acrylamido-based materials derived via sequential modification with n-butylamine and 5-aminotetrazole. In all instances, the substitution reactions were quantitative as judged by FTIR and 19 F NMR spectroscopies.…”

“…For example, all the polymer-Re hybrid materials possessed broad absorption bands centered around ≈370 nm which are associated with metal-toligand charge transfer transitions. [21,22] Hybrid materials with similar properties are also accessible via the chelation of the Re(CO) 3 (phen) fragment to RAFT-prepared pyridyl-functional copolymers. [31] The use of transition metal complexes as biological probes/imaging agents, including those attached to (co)polymers, is well-known.…”