Polymers Containing Nickel(II) Complexes of Goedken's Macrocycle: Optimized Synthesis and Electrochemical Characterization

Abstract

The synthesis and characterization of a new class of nickel-containing polymers is described. The optimized copolymerization of alkyne-bearing nickel(II) complexes of Goedken's macrocycle (4,11-dihydro-5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine) and brominated 9,9-dihexylfluorene produced polymers with potential application as functional redox-active materials. The title polymers exhibit electrochemically reversible, ligand-centered oxidation events at 0.24 and 0.73 V versus the ferrocene/ferrocenium redox couple. They also display exceptional thermal stability and interesting absorption properties due to the presence of the macrocyclic nickel(II) complexes and π-conjugated units incorporated in their backbones.

Synthesis, characterization, and preceramic properties of π-conjugated polymers based on Ni(II) complexes of goedken's macrocycle

“…Reagents were purchased from Sigma-Aldrich, Alfa Aesar, or Oakwood Chemical and used as received unless otherwise stated. 4-[(trimethylsilyl)ethynyl]-benzoyl chloride, 63 tetramethyldibenzo-tetraaza [14]annulene nickel(II), 64 2,7-dibromo-9,9-dihexylfluorene, 65 2-bromo-9,9-dihexylfluorene, 65 5, 59 6F, 59 1 H NMR spectra were referenced to residual CHCl 3 (7.27 ppm) and 13 C NMR spectra were referenced to CDCl 3 (77.0 ppm). Mass spectrometry data were recorded in positive-ion mode with a Bruker microTOF II instrument using electrospray ionization.…”

“…Polymers (6F, 6T, and 6B) containing 9,9-dihexylfluorene (F), 3-hexylthiophene (T), or 2,5-bis(hexyloxy)benzene (B) and a Ni(II) complex of Goedken's macrocycle (5) were synthesized using previously optimized polymerization conditions (Scheme 1). 59 These comonomers were chosen for polymerization due to their p-conjugated nature and ability to potentially solubilize the rigid, p-conjugated backbones of the targeted copolymers (Scheme 1). The monomers were combined in equimolar quantities and dissolved in a dimethylformamide (DMF), di-isopropylamine (DIPA), and water mixture (2:1:0.03).…”

“…38,[54][55][56][57][58] One such example was synthesized by Manners and coworkers, where molybdenum cyclopentadienyl (Cp) carbonyl was used to append two MoCp(CO) 2 groups to each repeating unit of the backbone of a polyferrocenylsilane (4) to produce metallopolymers with utility in UV-photolithography applications. 54 Herein, we build on our previously communicated results 59 by presenting an expansion of a series of p-conjugated polymers containing Ni(II) complexes of Goedken's macrocycle and their comprehensive characterization, including comparison to model compounds. These copolymers have been specifically targeted in an effort to combine the redox and charge transfer properties of Ni(II)-complexes of Goedken's macrocycle 60,61 with common traits associated with pconjugated organic polymers (e.g., low band-gaps, charge transport properties).…”

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“…B. Gilroy I am very lucky to have a hard-working and talented research team engaged in a variety of projects cen tered around the synthesis of functional molecular, poly meric, and nanostructured materials. Our current projects include: the synthesis and characterization of stable verdazyl radical polymers for use as hydrophobic hole transport ma terials (Figure 1), 1 the production of highly metallized phos phonium polymers as precursors to novel heterogeneous catalysts, 2 the synthesis and evaluation of π-conjugated me tallopolymers for use in polymer based electronics, 3 and the development of redox active formazanate ligands for use in main group and transition metal coordination chemistry. 4,5 SYNFORM What is your most important scientific achieve ment to date and why?…”

Ring‐Opening Polymerisation of Low‐Strain Nickelocenophanes: Synthesis and Magnetic Properties of Polynickelocenes with Carbon and Silicon Main Chain Spacers

“…[10] Although the metallopolymer field has been subject to considerable recent progress, there have been few reports of well-characterised nickel-basedp olymers. Examples include p-conjugated nickel-polyyne copolymers, [11] metallophthalocyanine covalent organic frameworks, [12] bis(phosphine)nickel(II)-1,4-tetrafluorophenylene polymers, [13] polymers featuring nickel(II) complexes of Goedken's macrocycle (4,11-dihydro-5,7,12,14-tetramethyldibenzo [b,i] [1,4,8,11]tetraazacyclotetradecine), [14] and those included in Figure1. [15] ROP of strained [n]metallocenophanes has attracted extensive attention as ap athway to well defined metal-containing polymers and block copolymers.…”