9,10-Anthraquinones Disubstituted with Linear Alkoxy Groups: Spectroscopy, Electrochemistry, and Peculiarities of Their 2D and 3D Supramolecular Organizations.

Spectroscopic, electrochemical, and structural properties of 2,6-dialkoxy-9,10-anthraquinones (Anth-OCn, n = 4, 6, 8, 10, and 12) of increasing alkoxy substituents length were investigated. UV-vis spectroscopy showed a substitution-induced bathochromic shift of the least energetic band from 325 nm in the case of unsubstituted anthraquinone to ca. 350 nm for the studied derivatives. Similarly as unsubstituted anthraquinone, the studied compound showed two reversible one electron reductions to a radical anion and spinless anions, respectively. The first reduction was affected by electron-donating properties of the substituents, its potential being shifted to ca. -1.5 V (vs Fc/Fc+), i.e., by 80 to 95 mV as compared to the case of unsubstituted anthraquinone. This corresponded to a decrease of |EA| from 3.27 to 3.19-3.17 eV. The experimental spectroscopic and electrochemical data were in full agreement with the DFT calculations. The introduction of the alkoxy substituent improved solution processibility of the studied compounds and facilitated the formation of their ordered supramolecular 2D aggregation on HOPG as well as single crystal growth from solutions. Comparative structural investigations carried out on single crystals and monolayers deposited on HOPG revealed two, mutually related, effects of the substituent length on the resulting supramolecular organization. The first one concerns both the 2D organization in the monolayers and 3D molecular arrangement in crystals: increasing substituent length evolution of the structure occurs from herringbone-type to lamellar. The second effect, observed in monolayers of the derivatives with longer substituents, concerns gradual evolution of their lamellar structures with increasing substituent length. This evolution is induced by the structure of the graphite substrate and involves increasing correlation of the molecules orientation (anthraquinone cores as well as alkoxy substituents) with the symmetry of the graphite substrate. As a result, their 2D and 3D structures become dissimilar.

Self-Assembly Properties of Solution Processable, Electroactive Alkoxy, and Alkylthienylene Derivatives of Fused Benzoacridines: A Scanning Tunneling Microscopy Study.

Self-organization in mono- and bilayers on HOPG of two groups of benz[5,6]acridino[2,1,9,8-klmna]acridine derivatives, namely, 8,16-dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines with an increasing alkoxy substituent length and 8,16-bis(3- or 4- or 5-octylthiophen-2-yl)benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines, i.e., three positional isomers of the same benzoacridine, is investigated by scanning tunneling microscopy. The layers were deposited from a solution of the adsorbate (in hexane or dichloromethane) and imaged ex situ at molecular resolution. In all cases, the resulting two-dimensional (2D) supramolecular organization is governed by the interactions between large, fused heteroaromatic cores that form densely packed rows separated by areas covered by substituents. In 8,16-dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines, the alkoxy substituents, separating the rows of densely packed cores, are interdigitated. An increasing substituent length leads to an intuitively expected increase in this 2D unit cell parameter that corresponds to the orientation of the substituent in the monolayer. In the case of 8,16-bis(3- or 4- or 5-octylthiophen-2-yl)benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine positional isomers, the self-assembly processes are more complex. Although the determined 2D unit cell is in all cases essentially the same, the role of alkylthienylene substituents in layer formation is distinctly different. Thus, the formation of monolayers and bilayers is very sensitive to isomerism. 8,16-Bis(5-octylthiophen-2-yl)benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine is capable of forming the most stable monolayer and the most labile bilayer. In the case of 8,16-bis(3-octylthiophen-2-yl)benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine, an inverse phenomenon is observed leading to the most labile monolayer and the most stable bilayer. These differences are rationalized in terms of dissimilar molecular geometries of the studied isomers and different interdigitation patterns in their 2D supramolecular structures.

Supramolecular organization of liquid-crystal dimers - bis-cyanobiphenyl alkanes on HOPG by scanning tunneling microscopy.

2D supramolecular organization of a series of six cyanobiphenyls bimesogens deposited on highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM). The adsorbates are 1,ω-bis(4-cyanobiphenyl-4'-yl)alkanes (CBnCB) with different lengths of their flexible alkyl spacer (containing from 7 to 12 methylene groups). Microscopic investigations at the molecular resolution allow for detailed analysis of the effect of the alkyl spacer length on the type and the extent of the resulting 2D organization. It was demonstrated that bimesogens with shorter spacers (7 and 8 methylene units) organize in a similar manner characterized by the formation of two types of differently ordered monolayers: dense packed, wherein the molecules are oriented in one direction and ordered into parallel rows (layer structure), or less densely packed where they are organized into a chiral windmill-like structure. For derivatives with longer spacers (ranging from 9 to 12 methylene units) the additional effect of parity of carbon atoms in the spacer (even versus odd) is observed. In this range of the spacer lengths even membered bimesogens are also organized in a typical layer structure. However, odd-membered dimers exhibit a much more complex 2D supramolecular organization with a larger unit cell and a helical arrangement of the molecules. Careful comparison of this structure with the 3D structural data derived from the X-ray diffraction investigations of single crystals indicates that for these bimesogens a clear correlation exists between the observed complex 2D supramolecular organization in the monolayer and the organization in one of the crystallographic planes of the 3D nematic twist-bent phase.