Synthesis and Absorption Properties of Long Acenoacenes.

Acenes, polyaromatic hydrocarbons composed of linearly fused benzene rings have received immense attention due to their performance as semiconductors in organic optoelectronic applications. Their appealing physicochemical properties, such as extended delocalization, high charge carrier mobilities, narrow HOMO-LOMO gaps and partially radical character in the ground state make them very attractive targets for many potential applications. However, the intrinsic synthetic challenges of unsubstituted members such as high reactivity and poor solubility are still limiting factors for their wider exploitation. Herein, we report a simple general synthesis of a new family of angularly fused acenoacenes with improved stability compared to their isoelectronic linear counterparts. The synthesis and comprehensive characterization of pentacenopentacene, pentacenohexacene and hexacenohexacene, with lengths between decacene and dodecacene, are disclosed.

Spectra and nature of the electronic states of [1]Benzothieno[3,2-b][1]benzothiophene (BTBT): Single crystal and the aggregates.

Absorption, fluorescence, and phosphorescence spectra of single crystals of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and BTBT dispersed in frozen n-nonane, n-hexadecane, and dichloromethane matrices were studied at 5 K. Observation of a new absorption band and related changes in the fluorescence to phosphorescence intensity ratio, when the concentration of BTBT in the matrix increased above 10-4M, indicated the presence of BTBT aggregates. Quantum-chemistry calculations performed for the simplest aggregate, isolated dimer, showed that its structure is similar to the "herringbone" element in the BTBT crystal unit cell and the lowest electronic excited singlet state of the dimer has the intermolecular charge-transfer character. A qualitatively different nature of this state in dimers and in crystals, when compared with the situation in BTBT monomer [locally excited (LE) state], is associated with a decrease in the intersystem crossing yield. The structured vibronic structure of phosphorescence spectra in the studied systems indicated LE character of the triplet states.