Rhenium(I)-tetrazolato functional luminescent polymers: Organic-inorganic hybrids via RAFT and post-polymerization modification

Macromol. Rapid Commun.

Lowe

2022

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A new family of polyampholytes (PAMs) is described in which both the basic and acidic groups are based on nitrogen functional groups. Reversible addition-fragmentation chain transfer-prepared poly(pentafluorophenyl acrylate) is quantitatively modified sequentially with 3-picolylamine and 5-aminotetrazole, yielding the new well-defined statistical PAMs. Successful formation of the PAMs is confirmed via a combination of 19 F and 13 C NMR spectroscopy and FTIR. Aqueous electrophoresis indicates isoelectric points (pI) between 2.9 and 4.4 depending on copolymer composition. However, the pI is somewhat insensitive to the copolymer composition, a feature attributed to the similarity of the pK a s of the acid tetrazole species and the conjugate acid of the pyridyl repeat units.

Section: Resultsmentioning

confidence: 83%

Tetrazole as a Carboxylic Acid Isostere and the Synthesis of All Amine‐Based Polyampholytes

Nguyen

Macromol. Rapid Commun.

Lowe

2022

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“…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.…”

Section: Resultsmentioning

confidence: 99%

“…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.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we prepared new tetrazole‐functional (co)polymers accessed via the post‐polymerization modification of parent (co)polymers prepared by RAFT RDRP. In this initial report, [ 21 ] we detailed the synthesis of well‐defined statistical and block copolymers of styrene with 4‐cyanostyrene via trithiocarbonate‐mediated (co)polymerization. Following (co)polymer synthesis, the pendant cyano groups were converted to the corresponding tetrazole functional species via reaction with NaN 3 /NH 4 Cl.…”

Section: Introductionmentioning

confidence: 99%

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

Macro Chemistry & Physics

Hartnell

Hackett

et al. 2022

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Well‐defined copolymers containing luminescent iridium and hybrid iridium/rhenium fragments are prepared utilizing parent poly(n‐butyl acrylamide‐co‐N‐(1H‐tetrazol‐5‐yl) acrylamide) as macromolecular chelating species. The parent (co)polymers are prepared via the modification of a precursor poly(pentafluorophenyl acrylate) (polyPFPA) homopolymer, prepared by reversible addition‐fragmentation chain transfer polymerization, with n‐butylamine and 5‐aminotetrazole. Reaction of the parent copolymers with [Ir2(ppy)4(μ−Cl2)] (ppy = 2‐phenylpyridine) yields modified copolymers containing the Ir(ppy)2 fragment as a pendent group. Attachment of the Ir species is confirmed by a combination of photophysical studies, UV–Vis spectroscopy, and visually under irradiation with UV light. Importantly, it is demonstrated that the chelation of the Ir(ppy)2 fragment to a polymeric scaffold does not impact the fundamental photophysical properties of the Ir species. Attachment of a second luminescent metal species, Re(CO)3(phen) (phen = 1,10‐phenanthroline), gives hybrid materials containing Re(I) and Ir(III). The photophysical properties of these hybrid materials are consistent with the presence of both metal species and indicate the occurrence of energy transfer phenomena from the polymer‐bound Ir to Re metal centers. Finally, it is demonstrated that the Ir modified polymers and the Ir/Re hybrid materials offer potential in tissue imaging applications with scope to tune both luminescent properties and biological specificity as evidenced from preliminary brain tissue staining experiments.

Luminescent Copolymer‐Rhenium(I) Hybrid Materials via Picolylamine‐Modified Poly(pentafluorophenyl acrylate)

Fantini

Macro Chemistry & Physics

Massi

et al. 2020

The synthesis and photophysical properties of well‐defined polymer‐rhenium(I) hybrid materials is described. Reversible addition‐fragmentation chain transfer polymerization of pentafluorophenyl acrylate yields a parent homopolymer that serves as a reactive scaffold for the preparation of a series of new statistical copolymers containing pendent pyridyl functional groups in conjunction with various other repeat unit species. Attachment of [Re(CO)3(phen)]+ fragments via coordination through the pendent pyridyl groups yields the hybrid metal‐copolymer materials. Photophysical studies confirm successful rhenium coordination as judged from the absorption and emission profiles of the hybrid materials and further verify that the polymeric scaffold has no discernable effect on the luminescent properties of the coordinated rhenium species.