Flow-induced-crystallization: tailoring host–guest supramolecular co-assemblies at the liquid–solid interface

Hu, Yi; Zeng, Xingming; Sahare, Sanjay; Xie, Rongbin; Lee, Shern‐Long

doi:10.1039/d2na00160h

Cited by 7 publications

(12 citation statements)

References 38 publications

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“…In other words, the planar guest molecules help to maintain the bilayer template via host–guest van der Waals interaction, which has not been reported thus far to our knowledge. For a parallel test, the use of fullerene (e.g., C 60 ) failed to obtain the Kagomés although such a three-dimensional (3D) guest promoted bilayer formations of TPTC at the liquid–solid interface. , For saturated or a higher concentration condition (5.0 × 10 –4 M) of BPTC, coexisting phase separations of the bilayer Kagomé and BPTC domains were found frequently (Figure S8). Furthermore, it has been reported in the literature that COR dimers (bilayers) hardly form even in a cavity .…”

Section: Resultsmentioning

confidence: 99%

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STM Study of the Self-Assembly of Biphenyl-3,3′,5,5′-Tetracarboxylic Acid and Its Mixing Behavior with Coronene at the Liquid–Solid Interface

et al. 2023

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We report a scanning tunneling microscopy (STM) study of the molecular self-assembly of biphenyl-3,3′,5,5′tetracarboxylic acid (BPTC) at the octanoic acid/graphite interface. STM revealed that the BPTC molecules generated stable bilayers and monolayers under high and low sample concentrations, respectively. Besides hydrogen bonds, the bilayers were stabilized by molecular π-stacking, whereas the monolayers were maintained by solvent co-adsorption. A thermodynamically stable Kagoméstructure was obtained upon mixing BPTC with coronene (COR), while kinetic trapping of COR in the co-crystal structure was found by the subsequent deposition of COR onto a preformed BPTC bilayer on the surface. Force field calculation was conducted to compare the binding energies of different phases, which helped to provide plausible explanations for the structural stability formed via kinetic and thermodynamic pathways.

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Section: Resultsmentioning

confidence: 99%

“…Either flexible or robust molecular networks can allow the formation of co-crystals upon guest molecule incorporation. While multicomponent co-crystal systems have been reported, , examples of layered molecular structures involving more than one molecular building block are rare. − …”

Section: Introductionmentioning

confidence: 99%

STM Study of the Self-Assembly of Biphenyl-3,3′,5,5′-Tetracarboxylic Acid and Its Mixing Behavior with Coronene at the Liquid–Solid Interface

et al. 2023

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“…De Feyter et al , and Lee et al have demonstrated that solution flow direction could affect the adlayer assembly, structure, and stability. However, effects due to the direction of solution flow with respect to the substrate were not observed during these experiments.…”

Section: Resultsmentioning

confidence: 99%

“…(2) large scan areas should be imaged, and (3) regions surrounding the area of interest must be imaged to confirm uniform growth. De Feyter et al 58,59 and Lee et al 60 have demonstrated that solution flow direction could affect the adlayer assembly, structure, and stability. However, effects due to the direction of solution flow with respect to the substrate were not observed during these experiments.…”

Section: ■ Introductionmentioning

confidence: 99%

Influences on the Dynamics and Stability of Self-Assembly: Solvent, Substrate, and Concentration

2022

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The formation dynamics and stability of CoOEP at the solution/Au(111) interface are captured in situ using scanning tunneling microscopy (STM) in a dynamic solution flow cell at room temperature. The intermediate steps of self-assembly of CoOEP into an ordered monolayer were captured, and fractional coverage as a function of time was measured to extract characteristic parameters of the self-assembly process. Adlayer structure and formation under various solvents are compared to previous studies conducted on HOPG. The choice of substrate is found to have a dramatic influence on adlayer structure and stability. It was found that the CoOEP adlayer assembly on HOPG is an equilibrium process, and the monolayer can be readily formed within minutes of contact with solution (above a solvent-dependent threshold solution concentration); the dissolution of the formed adlayer is feasible, though the rate of dissolution is solvent-dependent. The assembly of an adlayer on Au(111) is kinetically driven, monolayer formation occurs within minutes, and dissolution is very slowonly minimal island dissolution was achieved after hours of pure solvent flow. Solvent incorporation of 1,2,4-trichlorobenzene (TCB) was observed to form a CoOEP pseudorectangular adlayer structure (REC) on both HOPG and Au(111), though a solvent-free pseudohexagonal structure (HEX) occurred at much higher concentrations of CoOEP on HOPG than on Au(111). This is likely due to the fact that CoOEP binds more strongly to Au(111) than HOPG, which promotes the REC to HEX transition on Au(111) at lower concentrations. Solvent incorporation of toluene (Tol) into a CoOEP adlayer on Au(111) was observed, but it did not incorporate into the adlayer on HOPG. There is a significant increase in the Arrhenius desorption rate factor (∼350) of toluene on HOPG relative to Au that is likely a driving factor for Tol coadsorption on Au. A very short-lived decane incorporated adlayer was also observed. The transformation on Au(111) from REC to HEX structure under 1 μM CoOEP in Tol occurred within ∼10 min, while under a solution of 470 μM CoOEP in TCB the transformation required ∼102 min. This variance is primarily due to the relative residence times of the solvent molecule on the Au(111) surface, where Tol has an estimated desorption rate 500 times greater than TCB. The unit cells of the CoOEP adlayer are also substrate-dependent. The commensurate TCB-incorporated REC structure on Au(111) contains two CoOEP but only one CoOEP on HOPG. Thus, the adlayer formation of CoOEP on Au(111) was more significantly affected by solvent than for adsorption on HOPG.

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“…Often, the addition of guest molecules to the host network (host-guest co-assembly) is investigated either on the solid surface or in solution. 83,84 Each of these has its unique advantages. 85 The specific interactions between the host and guest take place over atomic dimensions.…”

Section: Synergistic Effect Of Chemical Stimulimentioning

confidence: 99%

Surface supramolecular assemblies tailored by chemical/physical and synergistic stimuli: a scanning tunneling microscopy study

et al. 2023

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Flow-induced-crystallization: tailoring host–guest supramolecular co-assemblies at the liquid–solid interface

Abstract: Here, we report that using the method of simply contacting the sample solution droplet with a piece of tissue paper can create a solvent flow (capillary force). During this process,...

Cited by 7 publications

References 38 publications

STM Study of the Self-Assembly of Biphenyl-3,3′,5,5′-Tetracarboxylic Acid and Its Mixing Behavior with Coronene at the Liquid–Solid Interface

STM Study of the Self-Assembly of Biphenyl-3,3′,5,5′-Tetracarboxylic Acid and Its Mixing Behavior with Coronene at the Liquid–Solid Interface

Influences on the Dynamics and Stability of Self-Assembly: Solvent, Substrate, and Concentration

Surface supramolecular assemblies tailored by chemical/physical and synergistic stimuli: a scanning tunneling microscopy study

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