Ferrocene metallopolymers of intrinsic microporosity (MPIMs)

Zhai, Tianran; Ambrose, Kenson; Nyayachavadi, Audithya; Walter, Kelly G.; Feldblyum, Jeremy I.

doi:10.1039/d1cc05022b

Cited by 5 publications

(3 citation statements)

References 38 publications

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“…As a result, ferrocene-based metallopolymers are a distinctive class of functional materials that have gained much attention in recent years. [46][47][48][49][50] The possibility to tune the properties of ferrocene-based polymers and macromolecules relies on the redox activity of ferrocene, since this organometallic molecule undergoes fast one-electron oxidation to the positively charged ferrocenium form [Fe(η 5 -C 5 H 5 ) 2 ] + . By switching the redox state (Fe II /Fe III ) of the multiple ferrocenyl units (separately, or in a cooperative fashion) the charge, polarity, color, and hydrophilicity of the molecules may be controlled.…”

Section: Introductionmentioning

confidence: 99%

Electroactive sulfur-rich materials obtained via inverse vulcanization of a diallylsilyl-functionalized ferrocene

Vera-Tuset,

Mas-Ballesté,

Cuadrado

et al. 2024

Polym. Chem.

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Section: Introductionmentioning

confidence: 99%

Electroactive sulfur-rich materials obtained via inverse vulcanization of a diallylsilyl-functionalized ferrocene

Vera-Tuset,

Mas-Ballesté,

Cuadrado

et al. 2024

Polym. Chem.

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“…12 Polymers of intrinsic microporosity are known to enhance a broad array of sustainable energy technologies. 13,14 Although there is a general understanding of how each of these types of materials function independently, until recently, 15 few studies have investigated how the properties of all three would interact in a single material. For instance, incorporating metal centers into conjugated organic polymers has been shown to increase the conductivity of the material.…”

mentioning

confidence: 99%

“…The recent synthesis and characterization of Fc metallopolymers of intrinsic microporosity (MPIMs) has shown that it may be possible to combine the optoelectronic properties of conjugated organic polymers, the high conductance of Fc in molecular junctions, and the high surface area of intrinsically microporous materials within a single, soluble non-network polymer. 15 One area in which conjugated MPIMs may have a significant impact is in BHJ solar cells.…”

mentioning

confidence: 99%

Tunable Porosity and Conjugation in Ferrocene Polymers of Intrinsic Microporosity

Chua

Welch

Qian

et al. 2022

Preprint

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Ferrocene (Fc) metallopolymers of intrinsic microporosity (MPIMs) have recently been reported as soluble, porous, non-network polymers, with evidence of electron delocalization along the polymer backbone. The combination of these properties makes Fc-MPIMs ideal candidate materials for optoelectronic devices, and the ability to tune these properties would broaden the impact of these materials. In this work, density functional theory (DFT) calculations at the CAM-B3LYP/def2SVP level were carried out on Fc MPIM fragments to examine the effect of pendant functional groups on conformational stability and electron delocalization in these systems. The conformational stability of the Fc MPIMs can affect the porosity, and the electronic delocalization is related to the conjugation in the material. The Fc MPIM fragments are most stable when the dihedral angle between Fc cyclopentadienyl (Cp) rings is 11.5°. Pendant functional groups are found to affect the stability of the local minimum at 144°, with alkyl chains increasing the stability, and bulky tert-butyl and trifluoromethyl groups decreasing stability. It is also possible to tune the electron delocalization of the HOMO and LUMO across the molecule. The Fe center of the Fc moiety contributes to the frontier orbitals, which is expected to enhance electronic communication in the parent polymer. Time-dependent density functional theory calculations indicate the π→π^* transition is slightly affected by the orientation of the dihedral angle between Cp rings, but primarily depends on the electronic nature of the pendant group. This work shows that the conformational stability and orbital delocalization of a model Fc MPIM can be tuned by functionalization with different pendant groups.

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Synthesis of Thioalkynes by Desilylative Sonogashira Cross‐Coupling of Aryl Iodides and 1‐Methylthio‐2‐(trimethylsilyl)ethyne

2022

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1‐Methylthio‐2‐arylethynes were prepared in typically good to excellent yields from aryl iodides and 1‐methylthio‐2‐(trimethylsilyl)ethyne by a desilylative Sonogashira process employing Pd(PPh3)2Cl2 (1 mol %), CuI (10 mol %), and K2CO3 (6 eq) in MeOH‐Et3N‐THF (1 : 2 : 2) at rt for 16 h (16 examples, 31–96 % yield). Thienyl and pyridyl iodides (all regioisomers) were similarly converted to 1‐methylthio‐2‐heteroarylethynes (5 examples, 54–82 % yield). The process was extended with similar results to comparable thioalkynes substituted on sulfur by n‐alkyl, s‐alkyl, and aryl groups.

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Ferrocene metallopolymers of intrinsic microporosity (MPIMs)

Abstract: Ferrocene-containing polymers can simultaneously possess porosity, solubility, and intrachain electronic communication.

Cited by 5 publications

References 38 publications

Electroactive sulfur-rich materials obtained via inverse vulcanization of a diallylsilyl-functionalized ferrocene

Electroactive sulfur-rich materials obtained via inverse vulcanization of a diallylsilyl-functionalized ferrocene

Tunable Porosity and Conjugation in Ferrocene Polymers of Intrinsic Microporosity

Synthesis of Thioalkynes by Desilylative Sonogashira Cross‐Coupling of Aryl Iodides and 1‐Methylthio‐2‐(trimethylsilyl)ethyne

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