Cherish Nie

Poly(divinyloligocyclobutanes) (pDVOCBs) are a distinct class of butadiene-derived, chemically recyclable polyolefins prepared from iron-catalyzed [2 + 2] cycloaddition followed by ruthenium-catalyzed ADMET polymerization. These polymers are highly crystalline, with high melting temperatures and unique rotator phases. The high degree of crystallinity in these materials not only leads to high stiffness over a broad temperature range but also results in brittle failure for polymers of modest molecular weights. Iron-catalyzed cross-[2 + 2] cycloaddition of butadiene and α,ω-dienes was accomplished, where the number of methylene units between the four-membered rings was systematically varied. Subsequent ADMET polymerization of the resulting telechelic oligomers provided a new class of chemically recyclable polyolefins that exhibit distinct thermomechanical properties. Specifically, methylene units induce changes in crystallinity that, in combination with the increased molecular weight, favored the formation of stable necks upon tensile deformation, with ∼10× enhanced ductility and improved toughness compared to pDVOCB. Through combined experimental and computational studies, the effects of methylene spacers on the crystal-to-rotator transition of the cyclobutane polymers were established. Ultimately, these methylene-modified cyclobutane polymers expand the range of properties and potential applications of this class of recyclable polyolefins.

N-heterocyclic carbene (NHC)-supported nickel complexes were investigated for the oxidative ring-opening of vinylcyclobutane (VCB) and photocatalytic activity. Addition of VCB to in situ generated [(NHC)Ni(0)] compounds furnished (NHC)Ni(VCB)₂ that underwent oxidative addition and conversion to the corresponding Ni(II) alkyl, allyl-metallacycles. The (NHC)Ni(C₆H₁₀) metallacycles were isolated, characterized, and exhibited high thermal and chemical stability. Irradiation with visible light at ambient temperature produced a mixture of ethylene and 4-vinylcyclohexene and 1,5-cyclooctadiene, cycloaddition dimers of butadiene, arising from formal retro-[2 + 2] cycloaddition. A mixture of hexadiene products arising from β-H elimination from the metallacycle was also observed. Free ethylene also underwent a secondary reaction to form cyclopropane products through formal [2 + 1] cycloaddition. A series of sterically and electronically modified NHC ligands was evaluated to establish the structure-activity relationship governing the rate of photocatalytic conversion of VCB and the resulting product distribution. Isotopic labeling experiments, resting state analysis, and independent synthesis of a range of nickel bis(olefin) complexes provided insight into the mechanism of the reaction and origins of the organic product mixture. (NHC)Ni-catalysis was also applied toward the retro-[2 + 2] depolymerization of (1,n'-divinyl)-oligocyclobutane to butadiene dimers.

Thirteen boronated cyanometallates [M(CN-BR₃)₆]^3/4/5- [M = Cr, Mn, Fe, Ru, Os; BR₃ = BPh₃, B(2,4,6,-F₃C₆H₂)₃, B(C₆F₅)₃] and one metalloboratonitrile [Cr(NC-BPh₃)₆]^3- have been characterized by X-ray crystallography and spectroscopy [UV-vis-near-IR, NMR, IR, spectroelectrochemistry, and magnetic circular dichroism (MCD)]; CASSCF+NEVPT2 methods were employed in calculations of electronic structures. For (t_2g)⁵ electronic configurations, the lowest-energy ligand-to-metal charge-transfer (LMCT) absorptions and MCD C-terms in the spectra of boronated species have been assigned to transitions from cyanide π + B-C borane σ orbitals. CASSCF+NEVPT2 calculations including t_1u and t_2u orbitals reproduced t_1u/t_2u → t_2g excitation energies. Many [M(CN-BR₃)₆]^3/4- complexes exhibited highly electrochemically reversible redox couples. Notably, the reduction formal potentials of all five [M(CN-B(C₆F₅)₃)₆]^3- anions scale with the LMCT energies, and Mn(I) and Cr(II) compounds, [K(18-crown-6)]₅[Mn(CN-B(C₆F₅)₃)₆] and [K(18-crown-6)]₄[Cr(CN-B(C₆F₅)₃)₆], are surprisingly stable. Continuous-wave and pulsed electron paramagnetic resonance (EPR; hyperfine sublevel correlation) spectra were collected for all Cr(III) complexes; as expected, ¹⁴N hyperfine splittings are greater for (Ph₄As)₃[Cr(NC-BPh₃)₆] than for (Ph₄As)₃[Cr(CN-BPh₃)₆].