Tuning the Diradical Character of Pentacene Derivatives via Non-Benzenoid Coupling Motifs.

The development of functional organic molecules requires structures of increasing size and complexity, which are typically obtained by the covalent coupling of smaller building blocks. Herein, with the aid of high-resolution scanning tunneling microscopy/spectroscopy and density functional theory, the coupling of a sterically demanded pentacene derivative on Au(111) into fused dimers connected by non-benzenoid rings was studied. The diradical character of the products was tuned according to the coupling section. In particular, the antiaromaticity of cyclobutadiene as the coupling motif and its position within the structure play a decisive role in shifting the natural orbital occupancies toward a stronger diradical electronic character. Understanding these structure-property relations is desirable not only for fundamental reasons but also for designing new complex and functional molecular structures.

Push-pull amino-nitro helicenes: synthesis, (chir)optical properties and self-assembly into thin films.

A series of regioisomeric push-pull amino-nitro [6]helicenes and a related [7]helicene derivative were prepared and their racemates resolved into enantiomers. Compared to the parent helicenes, they exhibit red-shifted UV-Vis spectra, pronounced dipole moments, altered chiroptical properties such as remarkable optical rotatory power, and can form nanocrystalline Langmuir-Blodgett films.

Preparative-scale synthesis of nonacene.

During the last years we have witnessed progressive evolution of preparation of acenes with length up to dodecacene by on-surface synthesis in ultra-high vacuum or generation of acenes up to decacene in solid matrices at low temperatures. While these protocols with very specific conditions produce the acenes in amount of few molecules, the strategies leading to the acenes in large quantities dawdle behind. Only recently and after 70 years of synthetic attempts, heptacene has been prepared in bulk phase. However, the preparative scale synthesis of higher homologues still remains a formidable challenge. Here we report the preparation and characterisation of nonacene and show its excellent thermal and in-time stability.

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.

A Large Starphene Comprising Pentacene Branches.

Starphenes are attractive compounds due to their characteristic physicochemical properties that are inherited from acenes, making them interesting compounds for organic electronics and optics. However, the instability and low solubility of larger starphene homologs make their synthesis extremely challenging. Herein, we present a new strategy leading to pristine [16]starphene in preparative scale. Our approach is based on a synthesis of a carbonyl-protected starphene precursor that is thermally converted in a solid-state form to the neat [16]starphene, which is then characterised with a variety of analytical methods, such as 13 C CP-MAS NMR, TGA, MS MALDI, UV/Vis and FTIR spectroscopy. Furthermore, high-resolution STM experiments unambiguously confirm its expected structure and reveal a moderate electronic delocalisation between the pentacene arms. Nucleus-independent chemical shifts NICS(1) are also calculated to survey its aromatic character.

Chirality-Controlled Self-Assembly of Amphiphilic Dibenzo[6]helicenes into Langmuir-Blodgett Thin Films.

Racemic and highly enantioenriched 3-methoxycarbonyl, 3-carboxy, and 3-hydroxymethyl derivatives of dibenzo[6]helicene were prepared. The Langmuir layers of these helicenes were formed at the air-water interface and transferred onto solid substrates to afford Langmuir-Blodgett films, which were then studied by ambient atomic force microscopy and (chir)optical spectroscopy. Significant differences were found in the behaviour of the Langmuir layers as well as in the morphology, UV/Vis, electronic circular dichroism (ECD), and fluorescence spectra of the Langmuir-Blodgett thin films depending on the molecular chirality and nature of the polar group. The experimental results were supported by molecular dynamics simulations.

Taxonomic update of Clitocybula sensu lato with a new generic classification.

The taxonomy and phylogeny of the hydropoid clade (genera Clitocybula s.l., Megacollybia, Leucoinocybe gen. nov., Hydropus, Trogia, Gerronema, Porotheleum and Lignomphalia gen. nov.) in Europe is studied using morphological and molecular approaches; the first three genera in detail including all known European species. Only two European species remain in Clitocybula s.str., Clitocybula lacerata and Clitocybula familia. The European C. lacerata is a species complex which should be treated as C. lacerata agg. at the current state of knowledge. A neotype originating from type area was designated to fix the application of the name. The presence of American species Clitocybula abundans in Europe is insufficiently proved. "Clitocybula dryadicola Ë® belongs to the genus Hydropus, and Clitocybula tilieti has an unclear systematic position. The results showed that Megacollybia and Leucoinocybe represent independent genera separated from Clitocybula. The genus Leucoinocybe is validly published with two European species, Leucoinocybe lenta and Leucoinocybe taniae. "Clitocybula flavoaurantia" proved to be conspecific with the latter species. The genus Lignomphalia is published for "Pseudoomphalina lignicola", a lignicolous omphalinoid species. The Indian "Clitocybula sulcata" is transferred to Leucoinocybe and "Clitocybula atrialba" to Gerronema. The first European records of Megacollybia marginata are published.

Asymmetric Synthesis of Nonracemic 2-Amino[6]helicenes and Their Self-Assembly into Langmuir Films.

Alternative ways of preparing nonracemic 2-amino[6]helicene derivatives were explored. The enantioselective [2 + 2 + 2] cycloisomerization of a nonchiral triyne under Ni(cod)2/( R)-QUINAP catalysis delivered the enantioenriched (+)-( P)-2-aminodibenzo[6]helicene derivative in 67% ee. An ultimate "point-to-helical" chirality transfer was observed in the cyclization of enantiopure triynes mediated by Ni(CO)2(PPh3)2 affording (-)-( M)- or (+)-( P)-7,8-bis( p-tolyl)hexahelicen-2-amine in >99% ee as well as its benzoderivative in >99% ee. The latter mode of stereocontrol was inefficient for a 2-aminobenzo[6]helicene congener with an embedded five-membered ring. The rac-, (-)-( M)-, and (+)-( P)-7,8-bis( p-tolyl)hexahelicen-2-amines formed Langmuir monolayers at the air-water interface featuring practically identical surface pressure vs mean molecular area isotherms. The corresponding Langmuir-Blodgett films on quartz or silicon substrates were characterized by UV-vis/ECD spectroscopy and AFM microscopy, respectively.