Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical.

Properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF4(-) anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ∼0.1 V upon going from 1 to 1a. Unsuccessful attempts to prepare several other aryl substituted derivatives of 1 by the classical synthetic route are described in the Supporting Information .

Synthesis and photopolymerization of low shrinkage methacrylate monomers containing bulky substituent groups.

OBJECTIVES: This study was conducted to determine whether novel photopolymerizable formulations based on dimethacrylate monomers with bulky substituent groups could provide low polymerization shrinkage without sacrifice to degree of conversion, and mechanical properties of the polymers. METHODS: Relatively high molecular weight dimethacrylate monomers were prepared from rigid bisphenol A core groups. Photopolymerization kinetics and shrinkage as well as flexural strength and glass transition temperatures were evaluated for various comonomer compositions. RESULTS: Copolymerization of the bulky monomers with TEGDMA show higher conversion but similar shrinkage compared with Bis-GMA/TEGDMA controls. The resulting polymers have suitable mechanical strength properties for potential dental restorative materials applications. When copolymerized with PEGDMA, the bulky monomers show lower shrinkage, comparable conversion, and more homogeneous polymeric network structures compared with Bis-EMA/PEGDMA systems. SIGNIFICANCE: The novel dimethacrylate monomers with reduced reactive group densities can decrease the polymerization shrinkage as anticipated, but there is no significant evidence that the bulky substituent groups have any additional effect on reducing shrinkage based on the physical interactions as polymer side chains. The bulky groups improve the double bond conversion and help maintain the mechanical properties of the resulting polymer, which would otherwise decrease rapidly due to the reduced crosslinking density. Further, it was found that bulky monomers help produce more homogeneous copolymer networks.

Use of near-IR to monitor the influence of external heating on dental composite photopolymerization.

OBJECTIVES: This study was conducted to determine the effect of modest external heating on the photopolymerization kinetics and conversion of commercial dental composite restorative materials. METHODS: A transmission-mode, real-time near-infrared spectroscopic technique was used to monitor the photopolymerization process in the composite materials at various temperatures between 23 and 70 degrees C. Several light curing units, differing in spectral output and power densities were compared at the different cure temperatures. Several significantly different commercial composites were compared for their response. RESULTS: Regardless of the curing light or composite material used, photopolymerization at a moderate curing temperature of 54.5 degrees C resulted in significantly higher immediate and final conversion values compared with room temperature photocuring. Contrary to the room temperature cured materials, at the elevated cure temperature the extent of post-cure was minor and different curing lights produced very uniform conversion values within a given material. The time required to reach a given level of conversion, established as full conversion with the room temperature cure, was reduced typically by 80-90% using the elevated curing conditions. Complementary kinetic studies confirmed the effect of cure temperature on increasing the polymerization rate in dental composites as significant. SIGNIFICANCE: Increasing the temperature of composite resin within potentially biologically compatible limits can significantly influences resin polymerization. These increased rates and conversion could lead to improved properties of composite restorative materials.