Nanoscale tailoring of supramolecular crystals <i>via</i> an oriented external electric field

Zeng, Xingming; Khan, Sadaf Bashir; Lee, Shern‐Long

doi:10.1039/d0nr01946a

Cited by 19 publications

(47 citation statements)

References 38 publications

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“…Furthermore, this finding also contradicts a few previous literature reports that a steady pattern of TMA porous networks might trap guest molecules, irrespective of the electrical polarity of the substrate [ 138 ]. Recently, Shern-Long Lee and his colleagues studied electric field-induced, including temperature-assisted supramolecular phase alterations using TMA as a model structure at the liquid/solid interface [ 139 ]. They experimentally show that at a positive bias of a substrate, TMA nanostructure experienced a phase transformation from a porous network (22 °C) to a flower structure (45 °C), and finally forms compact (68 °C) assembly with increasing temperature as shown in Figure 9 a–c.…”

Section: Field-induced Supramolecular Phase Transitionsmentioning

confidence: 99%

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Supramolecular Chemistry: Host–Guest Molecular Complexes

Khan

Lee

2021

Molecules

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In recent times, researchers have emphasized practical approaches for capturing coordinated and selective guest entrap. The physisorbed nanoporous supramolecular complexes have been widely used to restrain various guest species on compact supporting surfaces. The host–guest (HG) interactions in two-dimensional (2D) permeable porous linkages are growing expeditiously due to their future applications in biocatalysis, separation technology, or nanoscale patterning. The different crystal-like nanoporous network has been acquired to enclose and trap guest molecules of various dimensions and contours. The host centers have been lumped together via noncovalent interactions (such as hydrogen bonds, van der Waals (vdW) interactions, or coordinate bonds). In this review article, we enlighten and elucidate recent progress in HG chemistry, explored via scanning tunneling microscopy (STM). We summarize the synthesis, design, and characterization of typical HG structural design examined on various substrates, under ambient surroundings at the liquid-solid (LS) interface, or during ultrahigh vacuum (UHV). We emphasize isoreticular complexes, vibrant HG coordination, or hosts functional cavities responsive to the applied stimulus. Finally, we critically discuss the significant challenges in advancing this developing electrochemical field.

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Section: Field-induced Supramolecular Phase Transitionsmentioning

confidence: 99%

“…It is experimentally evident that the change occurs at a positive bias of substrate and higher temperatures. These molecular dynamics pave the way towards a monitored supramolecular phase swapping under the influence of electrical-thermal stimuli [ 139 ].…”

Section: Field-induced Supramolecular Phase Transitionsmentioning

confidence: 99%

Supramolecular Chemistry: Host–Guest Molecular Complexes

Khan

Lee

2021

Molecules

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“…14,16,21,32,33 We recently reported the reversible STM-polarity-related phase transformations of TPTC. 11 Figure 1 shows TPTC assemblies that feature random tilling and close packing formed at the substrate of negative and positive STM biases, respectively. TPTC molecules can self-assemble into a glass-like randomtilling packing, as reported by Beton et al 34 Such packing includes five kinds of pores comprising diverse molecular linkages termed as triangle, parallelogram, arrow, semicircle, and star shape (see Supporting Information Figure S1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…For close packing, the types are expected to include the R, S, and head-to-head forms, as observed by STM (see our recent work); the unit-cell parameters of a, b, and α are 0.9 (±0.3) nm, 1.7 (±0.3) nm, and 87°(±2°), respectively. 11 Interestingly, Figure 1 represents the STM-bias-related behavior of TPTC assemblies. The packing can undergo phase transition between glass and crystal states by the selection of STM polarity, meaning its reversibility.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…As mentioned earlier, the R and S forms coexisted while the head-to-head packing hardly survived. 11 There is no preference to produce either R or S form, but it is still unclear why the head-to-head packing bears the lowest stability. The feature of fuzzy surfaces unveiled by STM can be referred to as the fast dynamics, including continuous desorption and adsorption of TPTC molecules on surfaces.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Dynamics of Supramolecular Crystal Growth at the Liquid–Solid Interface Studied via Scanning Tunneling Microscope and the Avrami Equation

Zeng

Wang

et al. 2021

J. Phys. Chem. C

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We report the study of supramolecular assembling from both experimental and theoretical points of view. A scanning tunneling microscope (STM) and the Johnson−Mehl−Avrami (JMA) equation were, respectively, used to reveal and to explain the "STM-directed" self-assembling of p-terphenyl-3,5,3′,5′-tetracarboxylic acid (TPTC) at the liquid−solid interface. The Avrami index helps in providing significant information regarding the surface supramolecular crystalline framework. It also helps us to calculate the domains of crystal growth, to distinguish the crystal development to be homogenous or heterogeneous, as well as to identify the dimension of the crystal growth. The JMA equation was also used to evaluate whether (i) the closepacking crystal of TPTC can develop into a single crystal or (ii) the porous networks of TPTC may hinder the close packing to form during its progression.

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Coronene and Bipyridine Derivatives Inducing Diversified Structural Transitions of Carboxylic Acids at the Liquid/Solid Interface

et al. 2022

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Comprehensive Summary In recent years, the construction of stable multicomponent assembled structures on surfaces and the exploration of the assembled mechanism have become research hotspots. In this paper, the azobenzene‐carboxylic acid called (E)‐4’,4”’‐(diazene‐1,2‐diyl) bis(([1,1’‐biphenyl]‐3,5‐dicarboxylic acid)) (H4DBBD) could self‐assemble into regular network structure at heptanoic acid/graphite via hydrogen bonding, and could be regulated into analogous kagomé network by coronene (COR) molecules. In addition, a series of bipyridine derivatives were further introduced to construct bi‐component systems with H4DBBD molecules, and successfully induced diversified structural transitions of H4DBBD on the graphite surface. Combined with scanning tunneling microscope (STM) and density functional theory (DFT) calculations, we have investigated the diversified structural transitions and analyzed the formation mechanism of the assembled systems.

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Nanoscale tailoring of supramolecular crystals via an oriented external electric field

Abstract: The oriented external electric field of a scanning tunneling microscope (STM) has recently been adapted for controlling the chemical reaction and supramolecular phase transition at surfaces with molecular precision.

Cited by 19 publications

References 38 publications

Supramolecular Chemistry: Host–Guest Molecular Complexes

Supramolecular Chemistry: Host–Guest Molecular Complexes

Dynamics of Supramolecular Crystal Growth at the Liquid–Solid Interface Studied via Scanning Tunneling Microscope and the Avrami Equation

Coronene and Bipyridine Derivatives Inducing Diversified Structural Transitions of Carboxylic Acids at the Liquid/Solid Interface

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