Dibenzannulated peri-acenoacenes from anthanthrene derivatives.

A series of dibenzannulated phenyl-annulated [4,2]peri-acenoacenes have been synthesized in three straightforward steps from 4,10-dibromoanthanthrone (vat orange 3). The phenyl bisannulation of [4,2]peri-acenoacene provides extra stability by increasing the overall aromatic character of the molecules, and allows for a 45-80% increase of the molar extinction coefficient (ε) compared to their [5,2]peri-acenoacene isomers. Depending on the substituents attached to the π-conjugated core, some derivatives exhibit strong aggregation in the solid state with association constant (Ka) up to 255 M-1, resulting in a significant broadening of the absorption spectrum and a substantial decrease of the bandgap value (more than 0.3 V) from solution to the solid state. One [4,2]peri-acenoacene derivative was doubly reduced using cesium and the crystal structure of the resulting salt has been obtained. Field-effect transistors showing a temperature-dependent hole mobility have been tested.

Annulated Azuleno[2,1,8-ija]azulenes: Synthesis and Properties.

Non-alternant non-benzenoid hydrocarbons exhibit very different optical and electronic properties than their well-studied benzenoid analogues. However, preparing such structures with extended conjugation length, remains challenging. Herein, we report the synthesis and properties of azuleno[2,1,8-ija]azulene derivatives using a two-step sequence involving a four-fold aldol condensation between aromatic dialdehydes and readily available tetrahydropentalene-2,5-(1H,3H)-dione. Molecules with band gap values ranging from 1.69 to 2.14 eV and molar extinction coefficients (ϵ) of nearly 3×105  M-1 cm-1 have been prepared. These annulene-like structures exhibit significant diatropic ring currents (aromatic), as supported by 1 H NMR spectroscopy and DFT calculations. Field-effect transistors (OFETs) using azuleno[2,1,8-ija]azulene derivatives as semiconductors exhibit charge mobility values of up to 0.05 cm2  V-1 s-1 .

Interfacial Synthesis of Layer-Oriented 2D Conjugated Metal-Organic Framework Films toward Directional Charge Transport.

The development of layer-oriented two-dimensional conjugated metal-organic frameworks (2D c-MOFs) enables access to direct charge transport, dial-in lateral/vertical electronic devices, and the unveiling of transport mechanisms but remains a significant synthetic challenge. Here we report the novel synthesis of metal-phthalocyanine-based p-type semiconducting 2D c-MOF films (Cu2[PcM-O8], M = Cu or Fe) with an unprecedented edge-on layer orientation at the air/water interface. The edge-on structure formation is guided by the preorganization of metal-phthalocyanine ligands, whose basal plane is perpendicular to the water surface due to their π-π interaction and hydrophobicity. Benefiting from the unique layer orientation, we are able to investigate the lateral and vertical conductivities by DC methods and thus demonstrate an anisotropic charge transport in the resulting Cu2[PcCu-O8] film. The directional conductivity studies combined with theoretical calculation identify that the intrinsic conductivity is dominated by charge transfer along the interlayer pathway. Moreover, a macroscopic (cm2 size) Hall-effect measurement reveals a Hall mobility of ∼4.4 cm2 V-1 s-1 for the obtained Cu2[PcCu-O8] film. The orientation control in semiconducting 2D c-MOFs will enable the development of various optoelectronic applications and the exploration of unique transport properties.