Thermodynamic versus kinetic control in self-assembly of zero-, one-, quasi-two-, and two-dimensional metal-organic coordination structures

Lin, Tao; Wu, Qi; Liu, Jun; Shi, Zhenming; Liu, Pei Nian; Lin, Nian

doi:10.1063/1.4906174

Cited by 27 publications

(24 citation statements)

References 35 publications

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“…This suggests that the nodes contain more than one metal atom, but probably not more than a dozen: the physical size of clusters much larger than this would not be able to accommodate the observed elongation along the [010] surface direction. Along the [- [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] direction, the BPDCA molecule and the metal cluster are not able to form a structure with a matching lattice periodicity (see Figure 8b). Energetically this complex is more than 2 eV less favorable than the structure along the [010] direction.…”

Section: Co-adsorption Of Bpdca and Fementioning

confidence: 96%

Deposition Order Controls the First Stages of a Metal–Organic Coordination Network on an Insulator Surface

et al. 2016

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We report on first stages towards the formation of a surface-confined metal-organic coordination network (MOCN) by sequential deposition of biphenyl-4,4'-dicarboxylic acid and iron atoms on the surface of a bulk insulator, calcite (10.4). The influence of the deposition order on the structure formation is studied by non-contact atomic force microscopy operated in ultra-high vacuum at room temperature. It is found that sequential deposition facilitates MOCN formation when the organic linker molecules are first adsorbed on the surface, followed by iron deposition. This observation is explained by first-principles computations, indicating that the metal-molecule interaction dominates over the molecule-molecule interaction on the surface. The observed MOCN islands are elongated in the [010] substrate direction, demonstrating a templating effect of the underlying substrate. This experimental finding is confirmed by calculations suggesting that the MOCN network matches the calcite lattice periodicity in [010] direction, but not in the [-4-21] direction. This work, thus, demonstrates the decisive influence of both deposition order and lattice matching on the formation of an extended MOCN on a bulk insulator surface.

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Section: Co-adsorption Of Bpdca and Fementioning

confidence: 96%

Deposition Order Controls the First Stages of a Metal–Organic Coordination Network on an Insulator Surface

et al. 2016

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“…In recent years, our groups and others have shown that programming organic molecules, through an appropriate geometrical combination of different peripheral recognition moieties, allows the formation of nanostructured surfaces featuring different architectures with various shapes and dimensions. [23][24][25][26][27][28] For example, exploiting the aptitude of pyridyl and cyanophenyl groups to engage in H-bonding, dipole-dipole or metal coordination interactions interactions, [29][30][31][32][33] functional porphyrin derivatives [34][35] featuring programmed geometries could be selectively organized in the presence of metal atoms as supramolecular polymers, 36 discrete macrocycles 37 or arrays with one 38 or two metal atoms. 31 In this context, photoactive polycyclic aromatic hydrocarbons (PAHs) are also of great interest due to their relevance in molecular electronics and photovoltaics.…”

mentioning

confidence: 99%

Supramolecular Spangling, Crocheting, and Knitting of Functionalized Pyrene Molecules on a Silver Surface

et al. 2016

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Pyrenes, as photoactive polycyclic aromatic hydrocarbons (PAHs), represent promising modules for the bottom-up assembly of functional nanostructures. Here, we introduce the synthesis of a family of pyrene derivatives peripherally functionalized with pyridin-4-ylethynyl termini and comprehensively characterize their self-assembly abilities on a smooth Ag(111) support by scanning tunneling microscopy. By deliberate selection of number and geometric positioning of the pyridyl-terminated substituents, two-dimensional arrays, one-dimensional coordination chains, and chiral, porous kagomé-type networks can be tailored. A comparison to phenyl-functionalized reference pyrenes, not supporting the self-assembly of ordered structures at low coverage, highlights the role of the pyridyl moieties for supramolecular crocheting and knitting. Furthermore, we demonstrate the selective spangling of pores in the two-dimensional pyrene assemblies by a distinct number of iodine atoms as guests by atomically resolved imaging and complementary X-ray photoelectron spectroscopy.

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“…This crystal size dependence on the band-gap and anisotropy absorbance of MIRO 101 can be explained in terms of two alternative orientations that tetrazole ligands adopt in the unit cell during growth, a type of polymorphism that is sensitive to the synthesis conditions. 49,50 Under its first reported synthesis conditions, 46 Zn(3-ptz) 2 (MIRO 101) was obtained in powder form. The x-ray diffraction pattern shows that the asymmetric unit of MIRO 101 exhibits static disorder in which the nitrogen atom of pyridyl group is located in the same crystallographic position of the carbon atom at position 3 in the pyridine, producing two types of pyridil orientations in the unit cell that coexist in a polycrystalline sample.…”

Section: Resultsmentioning

confidence: 99%

Anisotropic Band-Edge Absorption of Millimeter-Size Zn(3-Ptz)2 Single Crystal Metal-Organic Frameworks

Chi-Durán¹,

Fritz²,

Olaya³

et al. 2020

Preprint

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<div><div><div><p>Metal-organic frameworks (MOF) have emerged as promising tailor-design materials for developing next-generation solid-state devices with applications in linear and non-linear coherent optics. However, the implementation of functional devices is challenged by the notoriously difficult process of growing large MOF single-crystals of high optical quality. By controlling the solvo-thermal synthesis conditions, we succeed in producing large individual single crystals of the non-centrosymmetric MOF Zn(3-ptz)2 (MIRO-101) with deformed octahedron habit, and unprecedented surface areas of up to 37 mm<sup>2</sup>. We measure the polarized UV-visible absorption spectrum of individual Zn(3- ptz)2 single crystals across different lateral incidence planes. Millimeter size single crystals have band gap <i>E</i><i>g</i> = 3.32 eV, and exhibit anisotropic absorption in the band edge region near 350 nm, whereas polycrystalline samples are fully transparent in the same frequency range. Using solid-state density functional theory (DFT), the observed size dependence of the optical anisotropy is correlated with the preferred orientation adopted by freely rotating pyridyl groups under conditions of slow crystal self-assembly. Our work thus paves the way for the development of optical polarization switches based on metal-organic frameworks.</p></div></div></div>

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Thermodynamic versus kinetic control in self-assembly of zero-, one-, quasi-two-, and two-dimensional metal-organic coordination structures

Cited by 27 publications

References 35 publications

Deposition Order Controls the First Stages of a Metal–Organic Coordination Network on an Insulator Surface

Deposition Order Controls the First Stages of a Metal–Organic Coordination Network on an Insulator Surface

Supramolecular Spangling, Crocheting, and Knitting of Functionalized Pyrene Molecules on a Silver Surface

Anisotropic Band-Edge Absorption of Millimeter-Size Zn(3-Ptz)2 Single Crystal Metal-Organic Frameworks

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