Thermodynamic Controlled Hierarchical Assembly of Ternary Supramolecular Networks at the Liquid–Solid Interface

Abstract

Building and networking: Ternary supramolecular networks have been formed by coadsorption of dissimilar ternary building units at the liquid-solid interface. The structural characteristics of the networks undergo distinctive transformations as the building units change from binary to ternary components (see graphic).

Formation of Multicomponent Star Structures at the Liquid/Solid Interface

“…16,22,43,44 The main driving forces for this phenomenon are van der Waals interactions between a guest and the solid substrate surface and van der Waals interactions between a guest and the surrounding host matrix. For the later interactions, shape and size complementarity between the guest and the pore plays a crucial role.…”

“…For this purpose, self-assembly of hexaalkoxy substituted dehydrobenzo [12]annulene derivatives DBA-OCns was investigated at the tetradecane/graphite interface by means of scanning tunneling microscopy (STM). Monolayer structures were significantly influenced by co-adsorbed tetradecane molecules depending on the alkyl chains length (C 13 -C 16 ) of DBA-OCn. However, none of DBA-OCn molecules formed the expected trigonal complexes, indicating that an additional driving force is necessary for the formation of the trigonal complex and its assembly into the h-star structure.…”

“…More importantly, all attempts to observe the h-star structures from DBA-OC14 and DBA-OC16 in the presence of PDBA and HPEB (Figure S7) were never successful. These mixtures exhibited disordered structures and a small proportion of honeycomb structures, being consistent with the predictions based on the modeling studies.Though several examples of cooperative formations of 2D self-assemblies are known for twoand three-component systems,[5][6][7][8][9][10][11][12][13][14][15][16] only one example was reported by Zimmt et al for a fourcomponent system 17. In this case, a kinked diacetylene (DA) unit in alkyl chains linked to anthracene cores controls the order of four different molecules aligned in 1D rows via steric complementarity of the DA units 17.…”

Effect of bulky substituents on the self-assembly and mixing behavior of arylene ethynylene macrocycles at the solid/liquid interface

“…20 Molecular recognition plays an important role in the self-assembly of long range ordered supramolecular architectures, especially for multicomponent systems. Strong and highly directional hydrogen bonding or coordination interaction between the metal ion and ligand are generally preferred, [26][27][28][29] however, van der Waals forces could also yield sufficient recognition if carefully engineered. 30,31 For instance, complex three-, even up to four-component 2D crystals can be fabricated using DBA networks as a host.…”

Solution concentration controlled self-assembling structure with host–guest recognition at the liquid–solid interface

“…Moreover, apart from simple co-adsorption, it has been well-documented that the addition of guest molecules could overcome the energy loss caused by unoccupied areas, and subsequently form a specific network. [19][20][21][22] Considering that the H 3 TTCA honeycomb network was just linked by hydrogen bonds between -COOH groups, the inclusion of functional guest molecules would cause the rearrangement of the network. Our previous work reported that when H 3 TTCA was co-adsorbed with H 2 Pc, the H 2 Pc molecules tended to break the original H 3 TTCA chicken-wire structures and insert into the H 3 TTCA arrays because of the geometric mismatch of H 2 Pc and the H 3 TTCA pores.…”