Ice readily sheds from weak oil-swollen polymer gels but tends to adhere to mechanically robust coatings. This paper reports bilayer coatings that simultaneously possess high bulk hardness but low ice adhesion. These coatings are prepared by cocuring a triisocyanate, P#′-g-PDMS [a methacrylate polyol bearing poly­(dimethylsiloxane) (PDMS) side chains with # being 1, 2, or 3 and g denoting graft], and optionally a methacrylate polyol P#. The self-assembly of the system during coating formation yields a PDMS brush layer on the surface of the cross-linked polyurethane matrix. After the surface PDMS layer is lubricated with a silicone oil, this coating exhibits an ice adhesion τ that is 10 000-fold lower than that of a triisocyanate/P# coating. Ice slides under its own weight on such a coating at a tilt angle of 3°. Yet, the coating matrix is harder than poly­(ethylene terephthalate), a widely used plastic. Additionally, such a coating maintains its low τ values for more than 10 consecutive icing/deicing cycles. Subsequent increases in τ are reversed by allowing time for the replenishment of the depleted surface lubricant with that released from the coating matrix. This design opens the door for effective yet hard ice-shedding polymer coatings.

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The synthesis and characterization of a flexidentate pyridine-substituted formazanate ligand and its boron difluoride adducts, formed via two different coordination modes of the title ligand, are described. The first adduct adopted a structure that was typical of other boron difluoride adducts of triarylformazanate ligands and contained a free pyridine subsituent, while the second was formed via the chelation of nitrogen atoms from the formazanate backbone and the pyridine substituent. Stepwise protonation of the pydridine-functionalized adduct, which is essentially nonemissive, resulted in a significant increase in the fluorescence quantum yield up to a maximum of 18%, prompting the study of this adduct as a pH sensor. The coordination chemistry of each adduct was explored through reactions with nickel(II) bromide [NiBr(CHCN)], triflate [Ni(OTf)], and 1,1,1,4,4,4-hexafluoroacetylacetonate [Ni(hfac)(HO)] salts. Coordination to nickel(II) ions altered the physical properties of the boron difluoride formazanate adducts, including red-shifted absorption maxima and less negative reduction potentials. Together, these studies have demonstrated that the physical and electronic properties of boron difluoride adducts of formazanate ligands can be readily modulated through protonation and coordination chemistry.

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