Supramolecularly Engineered Functional π-Assemblies Based on Complementary Hydrogen-Bonding Interactions

Abstract

As details of exciting photonic and electronic properties arising from self-assembled functional dyes and related π-conjugated molecules become clearer, strategies for control of short and long-range chromophorechromophore orientations, regulation of ππ stacking arrangements, construction of self-organized nano-to-microscale architectures, diversification of materials properties, analysis of self-assembly pathways, and impartment of stimuli-responsive properties, are all becoming important issues in the research area of organic functional materials. This article focuses on the supramolecular assemblies of dyes and related π-conjugated systems whose organization processes are rationally controlled by complementary multiple hydrogen bonding (CMHB) interactions between melamine and barbituric acid/ cyanurate functional units. The article includes an overview of the construction principle of such systems, but special attention is focused on the work carried out in the authors's group (since 2002) using azobenzene, diarylethene, merocyanine, perylene bisimide dyes, and π-conjugated oligomers including oligo(p-phenylenevinylene), oligo-(p-phenyleneethynylene), and oligothiophenes. The design principles discussed in this account could open up new avenues to novel functional aspect and application of functional dyes and small-molecular π-conjugated systems.

Control over the Self‐Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π‐Stacks

“…[5][6][7][8][9][10][11][12][13][14][15][16][17] In order to achieve these functionalities, highlyordered, adaptive nanostructures formed via a cooperative supramolecular polymerization mechanism are highly desirable. 18 The introduction of orthogonal noncovalent interactions, 19 from which hydrogen bonding and combinations with other secondary interactions are by far the most exploited ones, 20 represents a rational means for this purpose.…”

Two-Dimensional (2D) Nanomaterials towards Electrochemical Nanoarchitectonics in Energy-Related Applications

“…303 These fabrication processes may be linked even with organic synthetic approaches 304,305 and supramolecular organization. 306,307 However, more important efforts for practical usage and industrial applications would be those for mass production, 63,308310 which would be a crucial step for further development of 2D materials. …”

Hybrid materials of 1D and 2D carbon allotropes and synthetic π-systems

“…While there are several strategies for preparing hybrid materials, molecular self-assembly using noncovalent interactions [5][6][7][8][9][10] is considered a simple and efficient approach to the preparation of hybrid materials [11][12][13][14][15][16] . The nanoscale and mesoscale ordering of the building blocks in these hybrid materials and the resultant morphological features determine their functional properties, which can be modified by exploiting the reversible and adaptive nature of noncovalent interactions 17,18 .…”

“…16b) 87 . Absorption and fluorescence studies showed that the aqueous dispersion of 40/SWNTs exclusively contained small-diameter nanotubes such as (6, 5: d = 0.757 nm) and (8,3: d = 0.782 nm), whereas the large diameter ones ( (7,5), (8,4), and (7, 6); d = 0.829, 0.840, and 0.895 nm) were removed from the assynthesized SWNTs samples by centrifugation. The rotation around the -C≡C-bonds of the phenyleneethynylene unit of 40 played a crucial role in the helical wrapping of SWNTs having a definite chirality.…”