Aromaticity is a key concept in organic chemistry. Even though this concept has already been theoretically extrapolated to three dimensions, it usually still remains restricted to planar molecules in organic chemistry textbooks. Stacking of antiaromatic π-systems has been proposed to induce three-dimensional aromaticity as a result of strong frontier orbital interactions. However, experimental evidence to support this prediction still remains elusive so far. Here we report that close stacking of antiaromatic porphyrins diminishes their inherent antiaromaticity in the solid state as well as in solution. The antiaromatic stacking furthermore allows a delocalization of the π-electrons, which enhances the two-photon absorption cross-section values of the antiaromatic porphyrins. This feature enables the dynamic switching of the non-linear optical properties by controlling the arrangement of antiaromatic π-systems on the basis of intermolecular orbital interactions.
Understanding of interactions among molecules is essential to elucidate the binding of pharmaceuticals on receptors, the mechanism of protein folding and self-assembling of organic molecules. While interactions between two aromatic molecules have been examined extensively, little is known about the interactions between two antiaromatic molecules. Theoretical investigations have predicted that antiaromatic molecules should be stabilized when they stack with each other by attractive intermolecular interactions. Here, we report the synthesis of a cyclophane, in which two antiaromatic porphyrin moieties adopt a stacked face-to-face geometry with a distance shorter than the sum of the van der Waals radii of the atoms involved. The aromaticity in this cyclophane has been examined experimentally and theoretically. This cyclophane exhibits three-dimensional spatial current channels between the two subunits, which corroborates the existence of attractive interactions between two antiaromatic π-systems.
Three-dimensional
aromaticity arising from the close stacking of
two antiaromatic π-conjugated macrocycles has recently received
considerable attention. Here, a cyclophane consisting of two antiaromatic
Ni(II) norcorrole units tethered with two flexible alkyl chains was
synthesized. The norcorrole cyclophane showed crystal polymorphism
providing three different solid-state structures. Surprisingly, one
of them adopted an aligned face-to-face stacking arrangement with
negligible displacement along the slipping axis. Although the exchange
repulsion between two π-clouds should be maximized in this orientation,
the π–π distance is remarkably close (3.258 Å).
Three-dimensional aromaticity in this conformation has been supported
experimentally and theoretically as evidenced by small bond length
alternations as well as the presence of a diatropic ring current.
An analogous cyclophane with two aromatic Ni(II) porphyrin units was
prepared for comparison. The porphyrin cyclophane exhibited a slipped-stacking
conformation with a larger displacement (2.9 Å) and a larger
interplanar distance (3.402 Å) without noticeable change of the
aromaticity of each porphyrin unit. In solution, the norcorrole cyclophane
forms a twist stacking arrangement with effective interplanar orbital
overlap and exists in an equilibrium between stacked and nonstacked
structures. Thermodynamic parameters of the stacking process were
estimated, revealing an inherently large attractive interaction operating
between two norcorrole units, which has been further supported by
energy decomposition analysis.
While hydrogenated porphyrins are abundant in natural and synthetic compounds, antiaromatic hydrogenated porphyrinoids have not been synthesized to date. Here, we report bacteriochlorin-like Ni(II) tetrahydronorcorrole complexes as the first examples of antiaromatic porphyrinoids that contain saturated pyrrole units.
Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3-cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16π conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO-LUMO gap and enhanced the near IR absorption property.
[Purpose] In sit-to-stand, the center of gravity (COG) is transferred from the buttocks to the narrow base of support of the feet, and raising the COG to the standing position is an action with a large dynamic demand, in which the motion of the trunk becomes important for COG transfer. The purpose of this study was to clarify, using young and elderly subjects, how the anterior movement of the trunk (split into trunk and pelvis segments) and lower limb joint movements influence the sit-to-stand action.[Method] Using a 3D motion analysis system and a force plate, we derived the angles of greatest trunk flexion (TA) and pelvic anterior inclination (PA), the fastest speed of center of mass motion (VCM), the absolute angles of the trunk and pelvis segments (TAA and PAA) and the relative angle of the trunk segment to the pelvis (RA) at the moment of buttocks lift-off, as well as the hip and knee joint moments at maximum extension (HM and KM). To find the differences between the actions of the young and the elderly we calculated the correlations between these items. [Results] For the young persons, we found significant negative correlations between KM and TA and RA of maximum flexion, and for the elderly, we found significant negative correlations between KM and TA and PA. In addition, despite the absence of differences in time taken for sit-to-stand, VCM in the forward direction of the elderly was faster than that of the young. [Conclusion] These results suggest the elderly use anterior inclination, and trunk and pelvis flexion to raise the speed of the center of mass (COM) in the forward direction to enable them to raise their COM, whereas the young use anterior inclination of the trunk segment to enable them to raise their COM.
From the analysis based on the broken-symmetry density functional theory (DFT) calculations, we in this study propose a strategy to enhance the open-shell characters and third-order nonlinear optical (NLO) properties of π-stacked dimers composed of antiaromatic molecules with weak open-shell characters. For this purpose, we here constructed cofacial π-stacked dimer models composed of aromatic and antiaromatic Ni porphyrins in order to examine the π-π stacking distance (R) dependence of the diradical characters (y) and static second hyperpolarizabilities (γ). The antiaromatic porphyrin dimers are found to have intermediate y around R∼3.3 Å, the result of which originates in the unique intermolecular interactions between the antiaromatic monomers. Static γ along the stacking direction of such antiaromatic porphyrin dimers with intermediate diradical characters are shown to be enhanced significantly as compared to those of the isolated monomers and the aromatic porphyrin dimers.
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