Homochiral and Heterochiral Self-Sorting Assemblies of Antiaromatic Ni(II) Norcorrole Dimers.

Recently, π-π stacked antiaromatic π-systems have received considerable attention because they can exhibit stacked-ring aromaticity due to substantial intermolecular orbital interactions. Here, we report three antiaromatic norcorrole dimers that self-assemble to form supramolecular architectures through chiral self-sorting. A 2,2'-linked norcorrole dimer with 3,5-di-tert-butylphenyl groups forms a π-stacked dimer both in solid and solution states via homochiral self-sorting. Its association constant in solution is (3.6±1.7)×105 M-1 at 20 °C. In the solid state, 3,3'-linked norcorrole dimers with 3,5-di-tert-butylphenyl and phenyl groups afford macrocyclic and helical supramolecular assemblies via heterochiral and homochiral self-sorting, respectively. Notably, the subtle modification in the substituent resulted in a complete change in the structure of the aggregates and the chiral self-sorting mode. The present findings demonstrate that structural manipulation in antiaromatic monomer units leads to the formation of various supramolecular assemblies on the basis of the attractive interactions between antiaromatic π-systems.

Molecular aggregation by hydrogen bonding in cold-crystallization behavior of mixed nucleobases analyzed by temperature-controlled infrared spectroscopy.

The cold-crystallization behaviors of dodecyl-substituted nucleobases (adenine, uracil, and thymine) were analyzed. The dodecyl derivative from uracil alone did not exhibit cold crystallization; however, a mixture of adenine and uracil derivatives at a molar ratio of 1 : 1 exhibited cold crystallization. These results are similar to the thermal behavior of dodecyl derivatives of adenine and thymine alone and in mixtures reported in a previous study. Temperature-controlled infrared spectroscopy was used to observe the molecular assembly states of the liquid, supercooled state, and cold-crystallized compounds. Hydrogen-bonded molecular pairs in the high-temperature liquid state, multiple hydrogen-bonded networks in the supercooled state, and reverse Hoogsteen-type complementary hydrogen bonds in cold-crystallized compounds were observed using infrared spectroscopy. The heterogeneity of the system, due to multiple types of hydrogen bonding, retarded the crystallization rate, resulting in supercooling and cold crystallization. Infrared spectroscopy, which can be used to measure the aggregation state of molecules, including the liquid and supercooled states, is an effective analytical method for clarifying the process of cold crystallization.

Determinant Factors of Three-Dimensional Aromaticity in Antiaromatic Cyclophanes.

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.

Three-dimensional aromaticity in an antiaromatic cyclophane.

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.

Synthesis of meso-Alkyl-Substituted Norcorrole-NiII Complexes and Conversion to 5-Oxaporphyrins(2.0.1.0).

The synthesis of antiaromatic NiII -norcorroles having primary, secondary, and tertiary alkyl groups at the reactive meso-positions was attempted. Reductive coupling of a NiII -dipyrrin precursor provided NiII -meso-dihexylnorcorrole, which underwent substantial degradation on silica gel. Introduction of tert-butyl groups was unsuccessful due to the difficult preparation of the corresponding dipyrrin precursor. Meanwhile, NiII -norcorroles with isopropyl and cyclohexyl groups were isolated as stable molecules under ambient conditions. Furthermore, we found that oxidation of NiII -meso-dialkylnorcorroles with hydrogen peroxide in the presence of sodium carbonate gave NiII -5-oxaporphyrins(2.0.1.0). In contrast, oxidation of NiII -meso-dimesitylnorcorrole under the same reaction conditions gave 10-oxaporphyrin(1.1.1.0). The contrasting reactivity can be attributed to the steric congestion around the meso-positions.

Theoretical Study on Open-Shell Singlet Character and Second Hyperpolarizabilities in Cofacial π-Stacked Dimers Composed of Weak Open-Shell Antiaromatic Porphyrins.

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 NiII 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.

Synthesis and Properties of meso-Arylated Corrphycenes.

A novel synthetic procedure for meso-aryl-substituted corrphycenes has been developed. Suzuki-Miyaura coupling of α,α'-dibromodipyrrin with vic-diborylalkene and o-diborylbenzene afforded ethenylene- and phenylene-bridged bisdipyrrins, respectively, which were transformed to the corresponding corrphycenes upon treatment with palladium acetate. The bridging units significantly affect the macrocyclic π-conjugation circuits, thus changing the aromatic characters and absorption features of corrphycenes.

Stacked antiaromatic porphyrins.

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.

Ni(II) tetrahydronorcorroles: antiaromatic porphyrinoids with saturated pyrrole units.

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.

Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles.

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.