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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates

Functions of clusters in nano or sub-nano scale significantly depend on not only kinds of their components but also arrangements, or symmetry, of their ...

Osaka University

Well-designed supramolecular clusters comprising triphenylmethylamine and various sulfonic acids.

Hierarchical classification and single-crystal X-ray analysis of unique pseudo-cubic hydrogen-bond networks composed of primary ammonium carboxylates were carried out. The networks consist of four carboxylate anions and four primary ammonium cations at the corners of the cube, and twelve charge-assisted N--H...O hydrogen bonds on the sides of the cube. The configuration of the carboxylate anions generates topological diversity in the network. The results of this hierarchical classification showed that pseudo-cubic hydrogen-bond networks composed of primary ammonium carboxylates can form nine topologically different networks. These pseudo-cubic networks are a subset of the networks formed by octameric water in the form of an "ice cube". The classification system can be applied to other pseudo-cubic networks in a similar way. A survey of crystal structures based on combinations of triphenylacetic acid with various alkylamines (carbon numbers up to eight) and examination of the CSD (Cambridge Structural Database) showed eight salts that form such networks in their crystal structures. These structures are classified into six topologically different networks. Similar networks composed of other salts are also discussed from a topological point of view.

Topological study of pseudo-cubic hydrogen-bond networks in a binary system composed of primary ammonium carboxylates: an analogue of an ice cube.

The supramolecular chirality of 1D ladder-type hydrogen-bond networks composed of primary ammonium carboxylates was determined based on topological considerations. Chirality in such networks is based on the absolute configuration of the primary ammonium cation, which arises from discrimination between the two oxygen atoms of the carboxylate anion. The configurations of the cations and anions generate topological diversity in the networks, which are classified into six subgroups. In the Cambridge Structural Database, salts based on ladder type 1 constitute over 70 % of salts with a 1D-ladder-type network. Ladder type 1, based on a 2(1)-axis, is not superimposable on its mirror image, which leads to the first definition of right- or left-handedness of 2(1)-helicity on the basis of supramolecular tilt chirality. Helical assemblies of 2(1)-type with triaxial chirality can be assembled in various ways to yield chiral bundles and crystals. On the basis of these considerations, we constructed clay mimic structures with several bundle patterns by connecting the hydrogen-bond networks by using bifunctional molecules. These results open up the possibility of in-depth crystal engineering based on hydrogen-bond topology.

Topological classification and supramolecular chirality of 21-helical ladder-type hydrogen-bond networks composed of primary ammonium carboxylates: bundle control in 21-helical assemblies.

Supramolecular hidden chirality of hydrogen-bonded (HB) networks of primary ammonium carboxylates was exposed by advanced graph set analysis from a symmetric viewpoint in topology. The ring-type HB (R-HB) networks are topologically regarded as faces, and therefore exhibit prochirality and positional isomerism due to substituents attached on the faces. To describe the symmetric properties of the faces, additional symbols, Re (right-handed or clockwise), Si (left-handed or anticlockwise), and m (mirror), were proposed. According to the symbols, various kinds of faces were classified based on the symmetry. This symmetry consideration of the faces enables us to precisely evaluate supramolecular chirality, especially its handedness, of 0D-cubic, 1D-ladder and 2D-sheet HB networks that are composed of the faces. The 1D-ladder and 2D-sheet HB networks generate chirality by accumulating the chiral faces in 1D and 2D manners, respectively, whereas 0D-cubic HB networks generate chirality based on combinations of eight kinds of faces, similar to the chirality of dice.

Tetsuharu Yuge

Department of Material and Life Science,
Graduate School of Engineering,
Department of Material and Life Science, Graduate School of Engineering

Osaka University

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates

Tetsuharu Yuge

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Material and Life Science,Graduate School of Engineering,Department of Material and Life Science, Graduate School of Engineering

Osaka University

Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates

Department of Material and Life Science,
Graduate School of Engineering,
Department of Material and Life Science, Graduate School of Engineering