Model compounds and monomers for phenylene ether carboranylene ketone (PECK) polymer synthesis: preparation and characterization of boron-arylated ortho-carboranes bearing carboxyphenyl, phenoxyphenyl or benzoylphenyl substituents

Ortho‐Carborane‐Functionalized Luminescent Polyethylene: Potential Chemodosimeter for the Sensing of Nucleophilic Anions

“…The identity of the copolymers has been fully characterized by NMR spectroscopy. For example, the 1 H, 13 C, and 11 B NMR spectra of ECBO3 are displayed in Figure 1. The 1 H NMR spectrum (bottom) showed that the resonances at d = 2.23 ppm and d = 1.64 ppm, which corresponed to the protons at the 1 and 2 positions of the side-chain, respectively, were well-resolved from the peaks (d 1.2~1.5 ppm) for the polyethylene backbone.…”

“…Polymer Analysis 1 H and 11 B NMR spectra of the polymers were recorded on a Bruker Spectrospin 400 spectrometer at 100 8C. 13 C NMR spectra were recorded on a Bruker AMAX 500 ( 13 C; 125.77 MHz) spectrometer at 120 8C with a 908 pulse angle, 2 s acquisition time, and 8 s relaxation delay. The samples were dissolved in C 2 D 2 Cl 4 (for 1 H, ca.…”

“…The co-monomer contents in the polymers were determined from 1 H NMR spectra. 13 C NMR peak assignments of the polymers in the aliphatic region were made analogously according to literature values. [21] The molecular weight (M w and M n ) and polydispersity index (PDI, M w /M n ) of the polymers were analyzed by high temperature gel-permeation chromatography (GPC) on Polymer Laboratories PL 220 at 160 8C in 1,2,4-trichlorobenzene and calibrated using narrow polystyrene standards as a reference.…”

“…Whilst a number of studies on the design and synthesis of ortho-carborane-based compounds have focused on small molecular systems, polymers bearing carborane moieties are recently attracting great interest because the incorporation of carborane moieties into a polymer backbone could lead to the modulation of the electronic and optical properties of the polymer. Although the majority of polymeric carboranes developed so far have been utilized in main-chain, conjugate polymers, [5,13] the development of side-chain polymers has rarely been reported; [6,14] this scarcity is in spite of various advantages of this type of polymer including the ability to control the polymer architecture in terms of molecular weight, functionality, and the degree of incorporation that may lead to intriguing properties.In this regard, polyolefins with pendant ortho-carboranemoieties can be considered as a novel class of such sidechain carboranyl polymers. As single-site catalytic systems based on Group 4 organometallic complexes have been an effective and straightforward method for the preparation of functionalized polyolefins, [15][16][17] it could be anticipated that the catalytic (co)polymerization of a-olefins bearing electron-deficient, bulky carborane groups may lead to the production of carboranyl polymers with well-defined structures.…”

Unsymmetrical p‐Carborane Backbone as a Linker for Donor–Acceptor Dyads

“…Such applications range from those of BNCT (boron neutron-capture therapy) in medicine [2] to those in the synthesis of superacids. [3] Partial substitution of boron by carbon gives rise to the related carboranes, which, in functionalised forms, are important building blocks for the engineering of soft matter, [4] polymers, [5] nonlinear materials, [6] rigid rods [7] and self-assembled molecular structures. [8] Carboranes of the closo form, such as 1,12-dicarbadecaborane (C 2 B 10 H 12 in Scheme 1) are geometrically rigid species with an electronic structure making them optically transparent and redox inactive.…”