Physical properties of active materials built up from small molecules are dictated by their molecular packing in the solid state. Here we demonstrate for the first time the growth of n-channel single-crystal field-effect transistors and organic thin-film transistors by sublimation of 2,6-dichloro-naphthalene diimide in air. Under these conditions, a new polymorph with two-dimensional brick-wall packing mode (b-phase) is obtained that is distinguished from the previously reported herringbone packing motif obtained from solution (a-phase). We are able to fabricate single-crystal field-effect transistors with electron mobilities in air of up to 8.6 cm 2 V À 1 s À 1 (a-phase) and up to 3.5 cm 2 V À 1 s À 1 (b-phase) on n-octadecyltriethoxysilane-modified substrates. On silicon dioxide, thin-film devices based on b-phase can be manufactured in air giving rise to electron mobilities of 0.37 cm 2 V À 1 s À 1 . The simple crystal and thin-film growth procedures by sublimation under ambient conditions avoid elaborate substrate modifications and costly vacuum equipment-based fabrication steps.

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Single crystal X-ray analysis reveals a flat perylene π-scaffold for a perylene bisimide bearing bulky 2,6-diphenylphenoxy substituents at the 1,7 bay positions. The flat structure provides sharp vibronic progressions in the absorption and fluorescence spectra, the sterical shielding outstanding fluorescence quantum yields in the solid state.

We have synthesized a series of dipolar squaraine dyes that contain dicyanovinyl groups as acceptor and benzannulated five-membered ring heterocycles with alkyl chains of varied length as donor moieties. Based on these squaraines, thin-film transistors (TFT) were fabricated by spin coating and solution shearing. Moreover, with one of these squaraine derivatives vacuum-deposited TFTs were prepared as well. Our detailed studies revealed that the transistor performance of the present series of squaraines is strongly dependent on their structural features as well as on the processing method of thin films. Thus, solution-sheared OTFTs of selenium squaraine bearing dodecyl substituents (denoted as Se-SQ-C12) performed best with a maximum hole mobility of 0.45 cm(2) V(-1) s(-1), which is by far the highest value yet reported for OTFTs based on squaraines. This value was even surpassed by vacuum-deposited thin films of n-butyl-substituted selenium squaraine Se-SQ-C4, the only sublimable compound in this series, exhibiting a record hole mobility of 1.3 cm(2) V(-1) s(-1). Furthermore, we have investigated the morphology of the thin films and the molecular packing of these squaraine dyes by optical spectroscopy, atomic force microscopy, and X-ray diffraction. These studies revealed a relationship between the molecular structure, packing motif, thin-film morphology, and transistor performance of the squaraine dyes. From the supramolecular point of view two packing features discovered in the single crystal structure of Se-SQ-C8 are of particular interest with regard to the structure-functionality relationship: The first is the slipped and antiparallel π-stacking motif which ensures cancellation of the molecules' dipole moments and J-type absorption band formation in thin films. The second is the presence of CN···Se noncovalent bonds which show similarities to the more common halogen-bonding interactions and which interconnect the individual one-dimensional slipped π-stacks, thus leading to two-dimensional percolation pathways along the source-drain direction.

A convenient and robust synthesis of bis[N,N'-diisopropylbenzamidinato(-)]silicon(II) (1), a donor-stabilized silylene, has been developed (35 g scale). To get further information about the reactivity profile of 1, a series of oxidative addition reactions were studied. Treatment of 1 with PhSe-SePh (Se-Se bond activation), C6F6 (C-F activation), and CO2 (C=O activation/cycloaddition) yielded the neutral six-coordinate silicon(IV) complexes 10, 11, and 13, respectively. Treatment of 1 with N2O resulted in the formation of the dinuclear five-coordinate silicon(IV) complex 12 (oxidative addition/dimerization), which contains a four-membered Si2O2 ring. Compounds 10-13 were characterized by NMR spectroscopic studies in the solid state and in solution and by crystal structure analyses. Silylene 1 is three-coordinate in the solid state (from crystal structure analysis) and exists as the four-coordinate isomer 1' in benzene solution (from computational studies). Based on state-of-the-art relativistic DFT analyses, the four-coordinate species 1' was demonstrated to be the thermodynamically favored isomer in benzene solution (favored by ΔG = 6.6 kcal mol(-1) over the three-coordinate species 1). The reason for this was studied by bonding analyses of 1 and 1'. Furthermore, the (29)Si NMR chemical shifts of 1 and 1' were computed, and in the case of 1' it was analyzed how this NMR spectroscopic parameter is affected by solvation. These studies further supported the assumption that the silylene is four-coordinate in solution.