Two-dimensional crystal engineering using halogen and hydrogen bonds: towards structural landscapes

Mukherjee, Arijit; Teyssandier, Joan; Hennrich, Gunther; Feyter, Steven De; Mali, Kunal S.

doi:10.1039/c7sc00129k

Cited by 53 publications

(50 citation statements)

References 55 publications

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“…Two‐component halogen‐bonded networks (Figure d, e) were formed akin to those displayed in Figure b, c. The honeycomb network obtained using 10 as the halogen bond donor was found to contain the halogen bond acceptor as a guest molecule. The formation of an auto host‐guest system in this case indicated that strength of halogen bonds in this specific case is not enough to sustain the open network and that the molecular guests are needed to stabilize the supramolecular assembly …”

Section: Halogen‐halogen Interactions and Halogen‐bonding In Self‐assmentioning

confidence: 98%

Halogen Bonding in Two‐Dimensional Crystal Engineering

2020

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Halogen bonds, which provide an intermolecular interaction with moderate strength and high directionality, have emerged as a promising tool in the repertoire of non‐covalent interactions. In this review, we provide a survey of the literature where halogen bonding was used for the fabrication of supramolecular networks on solid surfaces. The definitions of, and the distinction between halogen bonding and halogen‐halogen interactions are provided. Self‐assembled networks formed at the solution/solid interface and at the vacuum‐solid interface, stabilized in part by halogen bonding, are discussed. Besides the broad classification based on the interface at which the systems are studied, the systems are categorized further as those sustained by halogen‐halogen and halogen‐heteroatom contacts.

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Section: Halogen‐halogen Interactions and Halogen‐bonding In Self‐assmentioning

confidence: 98%

Halogen Bonding in Two‐Dimensional Crystal Engineering

2020

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“…Recognition interactions between functional groups on different tectons then form supramolecular synthons 9 linking the tectons together and driving self-assembly. Coordination bonds, [10][11] halogen bonds, [12][13] van der Waals interactions, [14][15] and even dynamic covalent bond formation 15 have all been employed as recognition interactions in the growth of complex 2D molecular networks. Hydrogen bonds in particular have been widely used as stabilizing interactions for 2D self-assembly.…”

Section: Introductionmentioning

confidence: 99%

“…Hydrogen bonds in particular have been widely used as stabilizing interactions for 2D self-assembly. 1,[5][6]12 A key example of the use of hydrogen bonds as molecular recognition interactions in 2D self-assembly is the triple hydrogen bond interaction formed between perylenetetracarboxylic diimide (PTCDI) and melamine. [17][18][19] The archetypal set of supramolecular synthons based on hydrogen bonds are those formed between the nucleobases of DNA.…”

Section: Introductionmentioning

confidence: 99%

Controlling the Two-Dimensional Self-Assembly of Functionalized Porphyrins via Adenine–Thymine Quartet Formation

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Toft

et al. 2018

J. Phys. Chem. C

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The development of supramolecular synthons capable of driving hierarchical two-dimensional self-assembly is an important step towards the growth of complex and functional molecular surfaces. In this work the formation of nucleobase quartets consisting of adenine and thymine groups was used to control the 2D self-assembly of porphyrins. Tetra-(phenylthymine) zinc porphyrin (Zn-tetra-TP) and tetra-(phenyladenine) porphyrin (tetra-AP) were synthesised and scanning tunneling microscopy (STM) experiments performed to visualize their self-assembly at the liquid-solid interface between an organic solvent and a graphite surface. Mono-component solutions of both Zn-tetra-TP and tetra-AP form stable 2D structures with either thyminethymine or adenine-adenine hydrogen bonding. Structural models based on STM data were validated using molecular mechanics (MM) simulations. In contrast, bi-component mixtures showed the formation of a structure with p4 symmetry consisting of alternating Zn-tetra-TP and tetra-AP molecules in a chessboard type pattern. The relative positions of the porphyrin components were identified from STM images via contrast changes associated with the zinc atom present in Zn-tetra-TP. MM simulations suggest that hydrogen bonding interactions within these structures are based on the formation of adenine-thymine (ATAT) quartets with Watson-Crick base pairing between adenine and thymine groups.

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“…Halogen-bonded (XB) molecular nanostructures 1,[7][8][9] are considerably less common in on-surface 2D systems but are increasingly being studied and seen as an important addition to the 'toolbox' of supramolecular assembly. Typically, iodine [10][11][12][13][14] and bromine atoms [15][16][17][18][19] are used as halogen bond donors due to their strong polarisability, but examples of chlorine 20 and fluorine 21,22 based assemblies have also been reported. Halogen bonds can also involve halogen atoms acting simultaneously as both donor and acceptor 11,16,17,23,24 , with the positive electrostatic potential of the sigma hole oriented towards the central 'belt' of negative electrostatic potential found on an adjacent halogen atom.…”

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confidence: 99%

Combining high-resolution scanning tunnelling microscopy and first-principles simulations to identify halogen bonding

et al. 2020

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Scanning tunnelling microscopy (STM) is commonly used to identify on-surface molecular self-assembled structures. However, its limited ability to reveal only the overall shape of molecules and their relative positions is not always enough to fully solve a supramolecular structure. Here, we analyse the assembly of a brominated polycyclic aromatic molecule on Au(111) and demonstrate that standard STM measurements cannot conclusively establish the nature of the intermolecular interactions. By performing high-resolution STM with a COfunctionalised tip, we clearly identify the location of rings and halogen atoms, determining that halogen bonding governs the assemblies. This is supported by density functional theory calculations that predict a stronger interaction energy for halogen rather than hydrogen bonding and by an electron density topology analysis that identifies characteristic features of halogen bonding. A similar approach should be able to solve many complex 2D supramolecular structures, and we predict its increasing use in molecular nanoscience at surfaces.

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Two-dimensional crystal engineering using halogen and hydrogen bonds: towards structural landscapes

Abstract: We apply the concepts of supramolecular synthons and structural landscapes to 2D crystallization at the solution–solid interface.

Cited by 53 publications

References 55 publications

Halogen Bonding in Two‐Dimensional Crystal Engineering

Halogen Bonding in Two‐Dimensional Crystal Engineering

Controlling the Two-Dimensional Self-Assembly of Functionalized Porphyrins via Adenine–Thymine Quartet Formation

Combining high-resolution scanning tunnelling microscopy and first-principles simulations to identify halogen bonding

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