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

Fantini, Gregorio; Dallerba, Elena; Massi, Massimiliano; Lowe, Andrew B.

doi:10.1002/macp.202000135

Cited by 3 publications

(3 citation statements)

References 41 publications

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“…[5][6][7][8] In fluid solution and in biological environments, the typical long-lived emitting states of Re I polypyridyl complex have been consistently employed as specific biological probes, [9][10][11][12] and for sensing of molecular oxygen and other triplet ground state molecules. [13][14][15] In more constrained media such as in polymeric matrixes, [16][17][18][19] variable photophysical behavior is observed as a function of the ligand structure and the specific linkage with the matrix. This flexibility has found interesting applications in LEDs.…”

Section: Introductionmentioning

confidence: 99%

Temperature Dependent Emission Properties of ReI Tricarbonyl Complexes with Dipyrido-Quinoxaline and Phenazine Ligands

Ramos¹,

Prado²,

Carmo³

et al. 2022

J. Braz. Chem. Soc.

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In this work, the emission properties of fac-[Re(CO)3(NN)(py)]+, NN = 1,10-phenanthroline (phen), dipyrido[3,2-f:2’,3’-h]quinoxaline (dpq) and dipyrido[3,2-a:2’3’-c]phenazine (dppz); py = pyridine were investigated in different temperatures, ranging from 80 to 300 K, and in different solvent mixtures and in polymethyl methacrylate. The changes observed in the emission quantum yields were rationalized based on a two-level excited state model, in which the nonemissive upper state is thermally populated and decays faster than the lowest lying emissive state. fac‑[Re(CO)3(dpq)(py)]+ is a metal-to-ligand charge transfer (MLCT) emitter as the complex with phen but exhibits smaller emission quantum yields, being more sensitive to the solvent. This behavior was rationalized by quantum-mechanical calculations including the spin-orbit coupling matrix elements, revealing that intersystem crossing from the lowest singlet excited state in fac- [Re(CO)3(dpq)(py)]+ likely occurs to triplet states lying at higher energies. Similar behavior were observed for fac-[Re(CO)3(dppz)(py)]+, although the later exhibits intraligand emission that are strongly quenched in fluid solutions by low-lying MLCT states. The fundamental studies carried out here provide new insights on the excited state dynamics of ReI complexes with dipyridoquinoxaline and phenazine ligands and can contribute for further advances on their application as luminescent probes.

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Section: Introductionmentioning

confidence: 99%

Temperature Dependent Emission Properties of ReI Tricarbonyl Complexes with Dipyrido-Quinoxaline and Phenazine Ligands

Ramos¹,

Prado²,

Carmo³

et al. 2022

J. Braz. Chem. Soc.

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“…[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. [32][33][34][35][36] For example, Redrado et al [37] recently described dual-function hybrid systems containing an organic chromophore and Ir(III) species for photodynamic therapy and bioimaging.…”

Section: Introductionmentioning

confidence: 99%

“…[ 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 ]…”

Section: Introductionmentioning

confidence: 99%

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

Dallerba

Hartnell

Hackett

et al. 2022

Macro Chemistry & Physics

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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.

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RAFT synthesis of thioether-based, AB diblock copolymer nanocarriers for reactive oxygen species–triggered release

Quek

Dabare

Bright

et al. 2021

Materials Today Chemistry

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

Cited by 3 publications

References 41 publications

Temperature Dependent Emission Properties of ReI Tricarbonyl Complexes with Dipyrido-Quinoxaline and Phenazine Ligands

Temperature Dependent Emission Properties of ReI Tricarbonyl Complexes with Dipyrido-Quinoxaline and Phenazine Ligands

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

RAFT synthesis of thioether-based, AB diblock copolymer nanocarriers for reactive oxygen species–triggered release

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