According to the Grotthuss–Draper law, light must be absorbed by a substrate to initiate a photoreaction. There have been several reports, however, on the promotion of photoreactions using hypervalent iodine during irradiation with light from a non‐absorbing region. This contradiction gave rise to a mystery regarding photoreactions involving hypervalent iodine. We demonstrated that the photoactivation of hypervalent iodine with light from the apparently non‐absorbing region proceeds via a direct S0→Tn transition, which has been considered a forbidden process. Spectroscopic, computational, and synthetic experimental results support this conclusion. Moreover, the photoactivation mode could be extended to monovalent iodine and bromine, as well as bismuth(III)‐containing molecules, providing new possibilities for studying photoreactions that involve heavy‐atom‐containing molecules.

Hypervalent iodines are widely used in organic chemistry, and their most important feature is the three‐center four‐electron bond. However, there have been few reports on the measurement of their bond dissociation enthalpy (BDE). Therefore, in many cases, BDE is estimated by computational calculations. However, the value of a calculated BDE usually varies depending on the choice of functional and basis set, and the best method for making an accurate evaluation of the three‐center four‐electron bond has not been determined. We succeeded in determining the best functional and basis set to calculate the three‐center four‐electron bond to within 0.79% error and 0.53 standard deviation. Using the optimal functional and basis set, the first and second BDEs of several hypervalent iodines are calculated, and as the effect of benzene substituents was investigated, negative correlation was observed in the Hammett plot. In addition, the effect of ortho‐substituent in cyclic hypervalent iodine was found to be significant. Furthermore, the decomposition route of hypervalent iodine is calculated. The value of a calculated BDE usually varies depending on the choice of functional and basis set. We succeeded in determining the best functional and basis sets to calculate the three‐center four‐electron bond of hypervalent iodine to within 0.79% error and 0.53 standard deviation. Using the optimal functional and basis sets, the first and second BDEs of several hypervalent iodines are calculated, and additionally, the decomposition route of hypervalent iodine is calculated.

Hybrid thermoplastic composites are getting attention in light weight applications. The manufacturing process of hybrid composites is that discontinuous fiber-reinforced thermoplastics are injected onto the textile-reinforced thermoplastics through injection over-molding. The key topic of this process is to achieve a reliable interfacial bonding strength, which has a strong dependence on the molding conditions. As a novel approach, we adopted a carbon nanotube-based thermoplastic film to make nanoscale interconnections between different layers by inserting films between the layers. In this work, the following influences were investigated with respect to the interlaminar shear strength by short beam shear test: the (i) existence, (ii) dispersion state, (iii) concentration of carbon nanotubes, and (iv) injection over-molding conditions. Furthermore, the delaminated surface after short beam shear test was assessed via SEM observation. Consequently, polypropylene-injected hybrid composite with 1 wt% carbon nanotubes exhibited a 52% increase in interlaminar shear strength compared with the specimen without carbon nanotubes. Additionally, the combination of short carbon fibers, which were filled in injected polypropylene, and carbon nanotubes drastically enhanced the interlaminar shear strength. The optimization of carbon nanotube dispersion and molding condition provides strong improvement of interlaminar shear strength. However, excessive addition of carbon nanotube deteriorates the interlaminar shear strength.

Benzophenone has an S 0 → S 1 absorption band at 365 nm. However, the rarely reported S 0 → T n transition occurs upon irradiation at longer wavelengths. Herein, we employed benzophenone as a catalyst and exploited its S 0 → T n transition in C(sp 3 )−H alkynylations with hypervalent iodine reagents. The selective benzophenone excitation prevented alkynylating reagent decomposition, enabling the reaction to proceed under mild conditions. The reaction mechanism was investigated by spectroscopic and computational studies.

Non‐precious metal electrocatalysts are under investigation as alternatives to platinum‐group metal electrocatalysts for the oxygen reduction reaction (ORR), which is required for cathode materials in fuel cells. Herein, we describe a new method for the synthesis of metal and nitrogen‐containing carbon (M/N/C) catalysts with high ORR activity using π‐expanded Fe(Salen) precursors. The Fe/N/C ORR catalysts were obtained by pyrolysis of a mixture of carbon support (Vulcan XC‐72R) and the iron complex precursors. The Fe/N/C catalyst prepared from N,N'‐bis(2‐hydroxy‐1‐naphthylidene)‐1,2‐phenylenediamino‐iron(III) chloride has an onset potential of 860 mV, which is positively shifted by 60 mV from that of the catalyst prepared from the simple Fe(Salen) complex. The catalyst promotes efficient four‐electron reduction in the ORR. XAFS and XPS studies reveal that the Fe/N/C catalysts have atomically‐dispersed iron active sites and that the activity depends on the high content of pyridinic nitrogen. This new methodology facilitates the design of non‐precious metal‐carbon catalysts with excellent ORR activity.