Carbonyl-Functionalized Cyclazines as Colorants and Air-Stable n-Type Semiconductors

Abstract

A series of π-extended cycl[3,3,2]azines (3) bearing additional carbonyl groups were synthesized via aldol condensations. Two strong electron acceptor molecules (4 and 5), with low-lying LUMO energy levels of -3.99 and -3.95 eV, respectively, were obtained. Organic thin-film transistors (TFTs) based on the cyanated cyclazine derivatives 5 were fabricated by vapor deposition, exhibiting extraordinarily stable n-type semiconductor character under ambient condition with the highest electron mobility of 0.06 cm V s consistently for more than 30 months.

Synthesis of a conjugated polymer with ring-fused pyridinium units via a postpolymerization intramolecular cyclization reaction

“…2e-g in DMF all showed strong absorption at 400-550 nm. The origin of this transition is not clearly understood, but similar DMFspecific behavior was also observed in another pyridiniumcontaining conjugated polymer [12]. PL measurements of 2e-g were performed in acetone.…”

“…Thus, the precise synthesis and characterization of N-doped PAHs are significantly important for the fundamental understanding of such materials, as well as their application as functional materials. Various N-doped PAHs have been reported with neutral [9][10][11][12] and cationic [12][13][14][15][16] nitrogen atoms in their structures.…”

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

“…A series of π-extended cycl[3,3,2]azines ( 217.2 – 4 ), structurally related to ullazines, were reported by Klauk, Müllen, and Li et al in 2018 ( Scheme 217 ). 414 Following an established route, the initial aldol condensation was carried out on 217.1 in imidazole solution, giving 217.2 in good yields. Malononitrile was reacted with 217.2 under acidic conditions, to produce the singly and doubly condensed products, 217.3 and 217.4 .…”

Delocalization Effects and Tunable Emission in a Class of Charged Cyclazines with Nitrogen on the Periphery

“…15−23 Apart from therapeutic relevance, they show interesting redox and photophysical properties and have potential use in the areas of molecular electronics, solar cells, etc. 18,24,25 An equally interesting group is their carbon analogues in which the central position is occupied by an sp 3 carbon. 26 Topological isomers of such systems, which possess centers carrying either lone pairs of electrons (heteroatom) or a vacant p-orbital in one of the peripheral positions, are also possible but are much less investigated.…”

“…Cyclazines, which possess a peri-fused π-framework with a nitrogen atom occupying the central position, have received special attention compared to simple aromatics. , Their syntheses generally involve cycloaddition of preformed indolizines or their analogues with suitable alkynes, but other routes employing properly substituted heterocyclic precursors through successive cyclization steps are also known. − Apart from therapeutic relevance, they show interesting redox and photophysical properties and have potential use in the areas of molecular electronics, solar cells, etc. ,, An equally interesting group is their carbon analogues in which the central position is occupied by an sp 3 carbon . Topological isomers of such systems, which possess centers carrying either lone pairs of electrons (heteroatom) or a vacant p-orbital in one of the peripheral positions, are also possible but are much less investigated .…”