Parallel-stacked aromatic molecules in hydrogen-bonded inorganic frameworks

Abstract

By precisely constructing molecules and assembling these into well-defined supramolecular structures, novel physical properties and functionalities can be realized, and new areas of the chemical space can be accessed. In both materials science and biology, a deeper understanding of the properties and exploitation of the reversible character of weak bonds and interactions, such as hydrogen bonds and π–π interactions, is anticipated to lead to the development of materials with novel properties and functionalities. We apply the hydrogen-bonded organic frameworks (HOFs) strategy to inorganic materials science using the cubic octamer of orthosilicic acid, [Si8O12][OH]8, as a building block, and find that various types of hydrogen-bonded inorganic frameworks (HIFs). We succeed in parallel π-stacking pure benzene, thiophene, selenophene, p-benzoquinone, thiophene·p-benzoquinone, and benzene·p-benzoquinone polymers infinitely. These polymers interact via their π-systems by taking advantage of the flexible pores of the three-dimensional nano-honeycomb HIFs, which consist of periodic wide and narrow segments.

Discrete Platinum(II/IV)–Arsenito Clusters with Pt–As and Pt–O Bonding: [PtIV(As3O6)2]2–, [Pt4II(H2AsO3)6(HAsO3)2]2–, and [Pt2IIAs6W4O28]10–

“…Hydrogen-bonded organic frameworks (HOFs) have received increasing attention and are expected to find applications in several fields . It appears that the HOF strategy can also be applied to inorganic materials . The formation of a stable 3D framework in K-Pt 4 As 8 is accompanied by a higher isolated yield and crystallinity, as well as aqueous insolubility.…”

Ferrocene-Containing Pseudorotaxanes in Crystals: Aromatic Interactions with Hammett Correlation

“…Thus, the energy differences among the possible interacted structures are small. Recently, parallel stacking of the aromatic rings ( Scheme 2 b) was found in the crystals of polyhedral oligomeric silsesquioxane (POSS) derivatives, although it was considered to be less stable than the others [ 63 ]. The combination of two aromatic rings at close positions was known to influence stability of their π–π stacking.…”

General Synthesis of MOF Nanotubes via Hydrogen-Bonded Organic Frameworks toward Efficient Hydrogen Evolution Electrocatalysts

“…HOFs are regularly constructed by organic or metal–organic building units via intermolecular hydrogen bonds. Currently, HOFs have received intensively increasing attention and are considered potentially tunable platforms for the construction of functional materials. − The hydrogen bonds endow HOFs with the traits of mild synthesis conditions, low directionality, solution processability, and structural flexibility, which leads us to postulate that organic linkers of MOFs can be assembled into HOFs to serve as templates and precursors for the synthesis of various low-dimensional MOFs. Considering the weak and flexible nature of hydrogen bonds, in theory, it is thermodynamically favorable to replace the hydrogen bonds with more stable coordination bonds.…”