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Cycloheptatrienyl (tropyl) molecules are representative non‐alternant hydrocarbons that offer interesting chemistry because of their unique structures and properties. However, there have been a limited number of polycyclic aromatic tropyl cations and radicals reported in the literature. Herein, we report the synthesis of a series of azahomocorannulene derivatives, where the key reactions are a 1,3‐dipolar cycloaddition of polycyclic aromatic azomethine ylides with dibenzotropone and a subsequent palladium‐catalyzed cyclization. X‐ray diffraction analysis revealed that the obtained azahomocorannulenyl cation and radical adopt planar structures and exhibit unique packing structures. Their electronic and optical properties were investigated experimentally and theoretically to reveal their aromatic character. [ABSTRACT FROM AUTHOR]

Abstract: Success in obtaining higher‐order twistarenes with precise structures is very important for fundamentally understanding the relationship between the structures and physical properties/optoelectronic applications. In this research, by using the advantages from a retro‐Diels–Alder process (clean reaction) and the cross‐conjugated nature of the pyrene unit, a novel dodeca‐twistarene was prepared for the first time. Its structure, confirmed by single‐crystal XRD analysis, indicates that it possesses a twisted angle (≈30°), and two neighboring molecules in the crystal lattice are perpendicular to each other because of the twisted character and the strong intermolecular CH–π interactions. However, its basic physicochemical properties suggest its instability in air derives from its elevated HOMO energy level, although NICS calculations confirm that the pyrene units contribution poorly to the π conjugation of the overall molecule. [ABSTRACT FROM AUTHOR]

Deprotonation of 1‐mesityl‐4,5‐diphenyl‐2‐imidazole 1 with nBuLi, followed by salt metathesis reaction with GeCl2·dioxane complex, led to the formation of the chlorogermyliumylidene 2 bearing two Ge–Cl units, which has been isolated and fully characterized by standard spectroscopic and X‐ray diffraction analysis. Structural and NMR spectroscopic data as well as computational studies revealed that the positive charge mainly resides on the Ge atom between two nitrogen atoms. Reduction of 2 with an excess amount of lithium metal resulted in Ge–Ge bond formation concomitant with elimination of one of the Ge atoms of 2, to give rise to the digermylenedilithium compound 3 involving intramolecular coordination of the imines and the lone pairs to the Li atoms. [ABSTRACT FROM AUTHOR]

A zwitterionic boraalkenyl boronium 3 was synthesized by reduction of cyclic (alkyl)(amino)carbene (cAAC) and trimethylphosphine (PMe3)-coordinated tetrabromodiborane 2 with KC8 in the presence of PMe3. Further reduction of 3 led to the formation of neutral allenic diborene 4. X-ray diffraction and computational studies revealed that 4 features the cumulated C=B and B=B double bonds. The reaction of 4 with four isonitrile molecules afforded a heterocycle 5 with the B2C3 five-membered ring, via a complete scission of the B=B bond of 4. [ABSTRACT FROM AUTHOR]

An autoionization of germanium dichloride/dioxane complex with an imino-N-heterocyclic carbene ligand ( L) afforded a novel germyliumylidene ion, [( L)GeCl]+[GeCl3]−, which was fully characterized. Reduction of the germyliumylidene ion with potassium graphite produced a cyclic species [( L)Ge], which can be viewed as both a Ge0 species and a mesoionic germylene. X-ray diffraction analysis and computational studies revealed one of the lone pairs on the Ge atom is involved in the π system on the GeC2N2 five-membered ring. It was also confirmed that the nucleophilic behavior of [( L)Ge] as a two lone-pair donor. [ABSTRACT FROM AUTHOR]