Boron is a unique element in terms of electron deficiency and Lewis acidity. Incorporation of boron atoms into an aromatic carbon framework offers a wide variety of functionality. However, the intrinsic instability of organoboron compounds against moisture and oxygen has delayed the development. Here, we present boron-doped graphene nanoribbons (B-GNRs) of widths of N=7, 14 and 21 by on-surface chemical reactions with an employed organoboron precursor. The location of the boron dopant is well defined in the centre of the B-GNR, corresponding to 4.8 atom%, as programmed. The chemical reactivity of B-GNRs is probed by the adsorption of nitric oxide (NO), which is most effectively trapped by the boron sites, demonstrating the Lewis acid character. Structural properties and the chemical nature of the NO-reacted B-GNR are determined by a combination of scanning tunnelling microscopy, high-resolution atomic force microscopy with a CO tip, and density functional and classical computations.

The chemistry of expanded porphyrins, which are higher homologues of porphyrins, has been intensively explored for the last three decades. Expanded porphyrins exhibit structures, electronic properties, coordination chemistry, and reactivities that are entirely different from those of porphyrins. Through these studies, it has become increasingly apparent that expanded porphyrins are attractive in views of aromaticity and multimetal coordination, or as functional dyes, nonlinear optical materials, ion receptors, or stable organic radicals. As such, we have continuously witnessed the emergence of expanded porphyrins that exhibit unprecedented structures and properties, as is highlighted by the facile realization of Möbius aromatic and even antiaromatic systems with twisted molecular structures. In this Review, the recent progress of the chemistry of expanded porphyrins after the seminal Review by Sessler and Seidel in 2003 is presented.

Luminescent mechanochromism has been intensively studied in the past few years. However, the difference in the anisotropic grinding and the isotropic compression is not clearly distinguished in many cases, in spite of the importance of this discrimination for the application of such mechanochromic materials. We now report the distinct luminescent responses of a new organic fluorophore, tetrathiazolylthiophene, to these stresses. The multichromism is achieved over the entire visible region using the single fluorophore. The different mechanisms of a blue shift by grinding crystals and of a red shift under hydrostatic pressure are fully investigated, which includes a high-pressure single-crystal X-ray diffraction analysis. The anisotropic and isotropic modes of mechanical loading suppress and enhance the excimer formation, respectively, in the 3D hydrogen-bond network.

meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1) have been examined by (1)H, (13)C, and (19)F NMR spectroscopies, UV-vis absorption spectroscopy, magnetic circular dichroism spectroscopy, and single-crystal X-ray diffraction analysis. All of these data consistently indicate that [28]hexaphyrins(1.1.1.1.1.1) in solution at 25 degrees C exist largely as an equilibrium among several rapidly interconverting twisted Möbius conformations with distinct aromaticities, with a small contribution from a planar rectangular conformation with antiaromatic character at slightly higher energy. In the solid state, [28]hexaphyrins(1.1.1.1.1.1) take either planar or Möbius-twisted conformations, depending upon the meso-aryl substituents and crystallization conditions, indicating a small energy difference between the two conformers. Importantly, when the temperature is decreased to -100 degrees C in THF, these rapid interconversions among Möbius conformations are frozen, allowing the detection of a single [28]hexaphyrin(1.1.1.1.1.1) species having a Möbius conformation. Detailed analyses of the solid-state Möbius structures of compounds 2b, 2c, and 2f showed that singly twisted structures are achieved without serious strain and that cyclic pi-conjugation is well-preserved, as needed for exhibiting strong diatropic ring currents. Actually, the harmonic-oscillator model for aromaticity (HOMA) values of these structures are significantly large (0.85, 0.69, and 0.71, respectively), confirming the first demonstration of stable Möbius aromatic systems consisting of free-base expanded porphyrins without the assistance of metal coordination.