Pathway Complexity in the Stacking of Imine-linked Macrocycles Related to Two-Dimensional Covalent Organic Frameworks

This work reports on the assembly of imine-linked macrocycles that serve as models of two-dimensional covalent organic frameworks (2D COFs). Interlayer interactions play an important role in the formation of 2D COFs, yet the effect of monomer structure on COF formation, crystallinity, and susceptibility to exfoliation are not well understood. For example, monomers with both electron-rich and electron-poor π-electron systems have been proposed to strengthen interlayer inter-actions and improve crystallinity. Here we probe these effects by studying the stacking behavior of imine-linked macrocycles that represent discrete models of 2D COFs. <div><br></div><div>Specifically, macrocycles based on terephthaldehyde (PDA) or 2,5-dimethoxyterephthaldehyde (DMPDA) stack upon cooling molecularly dissolved solutions. Both macrocycles assemble cooperatively with similar ΔHe values of -97 kJ/mol and -101 kJ/mol, respectively, although the DMPDA macrocycle assembly process showed a more straightforward temperature dependence. Circular dichroism spectroscopy performed on macrocycles bearing chiral side chains revealed a helix reversion process for the PDA macrocycles that was not observed for the DMPDA macrocycles. <br></div><div><br></div><div>Given the structural similarity of these monomers, these findings demonstrate that the stacking processes associated with nanotubes derived from these macrocycles, as well as for the corresponding COFs, are complex and susceptible to kinetic traps, casting doubt on the relevance of thermodynamic arguments for improving materials quality. <br></div>

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Pathway Complexity in the Stacking of Imine-linked Macrocycles Related to Two-Dimensional Covalent Organic Frameworks

10.26434/chemrxiv.7824707.v1 ◽

2019 ◽

Author(s):

Shiwei Wang ◽

Anton Chavez ◽

Simil Thomas ◽

Hong Li ◽

Nathan C. Flanders ◽

...

Keyword(s):

Temperature Dependence ◽

Structural Similarity ◽

Discrete Models ◽

Side Chains ◽

Two Dimensional ◽

Assembly Process ◽

Covalent Organic Frameworks ◽

Electron Systems ◽

Monomer Structure ◽

Kinetic Traps

This work reports on the assembly of imine-linked macrocycles that serve as models of two-dimensional covalent organic frameworks (2D COFs). Interlayer interactions play an important role in the formation of 2D COFs, yet the effect of monomer structure on COF formation, crystallinity, and susceptibility to exfoliation are not well understood. For example, monomers with both electron-rich and electron-poor π-electron systems have been proposed to strengthen interlayer inter-actions and improve crystallinity. Here we probe these effects by studying the stacking behavior of imine-linked macrocycles that represent discrete models of 2D COFs. <div><br></div><div>Specifically, macrocycles based on terephthaldehyde (PDA) or 2,5-dimethoxyterephthaldehyde (DMPDA) stack upon cooling molecu-lar dissolved solutions. Both macrocycles assemble cooperatively with similar ΔHe values of -97 kJ/mol and -101 kJ/mol, respectively, although the DMPDA macrocycle assembly process showed a more straightforward temperature dependence. Circular dichroism spec-troscopy performed on macrocycles bearing chiral side chains revealed a helix reversion process for the PDA macrocycles that was not observed for the DMPDA macrocycles. <br></div><div><br></div><div>Given the structural similarity of these monomers, these findings demonstrate that the stacking processes associated with nanotubes de-rived from these macrocycles, as well as for the corresponding COFs, are complex and susceptible to kinetic traps, casting doubt on the relevance of thermodynamic arguments for improving materials quality. <br></div>

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Temperature dependence of the compressibility of two-dimensional electron systems with long-range potential fluctuations in the quantum Hall effect regime

Journal of Experimental and Theoretical Physics ◽

10.1134/1.1777635 ◽

2004 ◽

Vol 98 (6) ◽

pp. 1222-1230 ◽

Cited By ~ 2

Author(s):

M. O. Dorokhova ◽

S. I. Dorozhkin

Keyword(s):

Temperature Dependence ◽

Hall Effect ◽

Long Range ◽

Quantum Hall Effect ◽

Quantum Hall ◽

Two Dimensional ◽

Electron Systems ◽

Dimensional Electron ◽

Potential Fluctuations ◽

Range Potential

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MAGNETIC FIELD INDUCED INSTABILITIES IN LOCALIZED TWO-DIMENSIONAL ELECTRON SYSTEMS

International Journal of Modern Physics B ◽

10.1142/s0217979209062232 ◽

2009 ◽

Vol 23 (12n13) ◽

pp. 2708-2712

Author(s):

MATTHIAS BAENNINGER ◽

ARINDAM GHOSH ◽

MICHAEL PEPPER ◽

HARVEY E. BEERE ◽

IAN FARRER ◽

...

Keyword(s):

Magnetic Field ◽

High Temperature ◽

Magnetic Fields ◽

Temperature Dependence ◽

Electron Density ◽

Two Dimensional ◽

Electron Systems ◽

Dimensional Electron ◽

Transport Studies ◽

Two Dimensional Electron Systems

The results of extensive transport studies in localized regime of mesoscopic two-dimensional electron systems (2DES) with varying disorder are presented. A quick overview of previously achieved result is given. The main focus is on the observation of density dependent instabilities manifested by strong resistance oscillations induced by high perpendicular magnetic fields B⊥. While the amplitude of the oscillations is strongly enhanced with increasing B⊥, their position in electron density remains unaffected. The temperature dependence of resistivity shows a transition from an activated behaviour at high temperature to a saturated behaviour at low T. In the positions of resistance minima, the T dependence can even become metal-like (dρ/dT > 0). The activation energies obtained from the high T behaviour exhibit a formation of plateaux in connection with the resistance oscillations when analyzed as a function of electron density. We suggest the interplay between a strongly interacting electron phase and the background disorder as a possible explanation for our observation.

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Temperature dependence of microwave-induced magnetoresistance oscillation in two-dimensional electron systems

Applied Physics Letters ◽

10.1063/1.3136757 ◽

2009 ◽

Vol 94 (23) ◽

pp. 232107 ◽

Cited By ~ 15

Author(s):

X. L. Lei ◽

S. Y. Liu

Keyword(s):

Temperature Dependence ◽

Two Dimensional ◽

Electron Systems ◽

Dimensional Electron ◽

Magnetoresistance Oscillation ◽

Two Dimensional Electron Systems

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Seeded Growth of Single-Crystal Two-Dimensional Covalent Organic Frameworks

10.26434/chemrxiv.5702437.v2 ◽

2017 ◽

Cited By ~ 1

Author(s):

Austin M. Evans ◽

Lucas R. Parent ◽

Nathan C. Flanders ◽

Ryan P. Bisbey ◽

Edon Vitaku ◽

...

Keyword(s):

Molecular Transport ◽

Controlled Synthesis ◽

Two Dimensional ◽

Covalent Organic Frameworks ◽

Seeded Growth ◽

Covalent Bonds ◽

Crystalline Materials ◽

Step Procedure ◽

Structures And Properties ◽

2D Polymer

<div> <div> <div> <p>Polymerizing monomers into periodic two-dimensional (2D) networks provides structurally precise, atomically thin macromolecular sheets linked by robust, covalent bonds. These materials exhibit desirable mechanical, optoelectrotronic, and molecular transport properties derived from their designed structure and permanent porosity. 2D covalent organic frameworks (COFs) offer broad monomer scope, but are generally isolated as polycrystalline, insoluble powders with limited processability. Here we overcome this limitation by controlling 2D COF formation using a two- step procedure. In the first step, 2D COF nanoparticle seeds are prepared with approximate diameters of 30 nm. Next, monomers are slowly added to suppress new nucleation while promoting epitaxial growth on the existing seeds to sizes of several microns. The resulting COF nanoparticles are of exceptional and unprecedented quality, isolated as single crystalline materials with micron-scale domain sizes. These findings advance the controlled synthesis of 2D layered COFs and will enable a broad exploration of synthetic 2D polymer structures and properties. </p> </div> </div> </div>

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Seeded Growth of Single-Crystal Two-Dimensional Covalent Organic Frameworks

10.26434/chemrxiv.5702437 ◽

2017 ◽

Author(s):

Austin M. Evans ◽

Lucas R. Parent ◽

Nathan C. Flanders ◽

Ryan P. Bisbey ◽

Edon Vitaku ◽

...

Keyword(s):

Molecular Transport ◽

Controlled Synthesis ◽

Two Dimensional ◽

Covalent Organic Frameworks ◽

Seeded Growth ◽

Covalent Bonds ◽

Crystalline Materials ◽

Step Procedure ◽

Structures And Properties ◽

2D Polymer

<div> <div> <div> <p>Polymerizing monomers into periodic two-dimensional (2D) networks provides structurally precise, atomically thin macromolecular sheets linked by robust, covalent bonds. These materials exhibit desirable mechanical, optoelectrotronic, and molecular transport properties derived from their designed structure and permanent porosity. 2D covalent organic frameworks (COFs) offer broad monomer scope, but are generally isolated as polycrystalline, insoluble powders with limited processability. Here we overcome this limitation by controlling 2D COF formation using a two- step procedure. In the first step, 2D COF nanoparticle seeds are prepared with approximate diameters of 30 nm. Next, monomers are slowly added to suppress new nucleation while promoting epitaxial growth on the existing seeds to sizes of several microns. The resulting COF nanoparticles are of exceptional and unprecedented quality, isolated as single crystalline materials with micron-scale domain sizes. These findings advance the controlled synthesis of 2D layered COFs and will enable a broad exploration of synthetic 2D polymer structures and properties. </p> </div> </div> </div>

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Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties

10.26434/chemrxiv.7766786.v2 ◽

2019 ◽

Author(s):

Simil Thomas ◽

Hong Li ◽

Raghunath R. Dasari ◽

Austin Evans ◽

William Dichtel ◽

...

Keyword(s):

Charge Transport ◽

Organic Semiconductors ◽

Density Functional ◽

Polymer Networks ◽

Two Dimensional ◽

Covalent Organic Frameworks ◽

X Ray Diffraction ◽

Zinc Porphyrin ◽

Design And Synthesis ◽

Predicted Values

<p>We have considered three two-dimensional (2D) π-conjugated polymer networks (i.e., covalent organic frameworks, COFs) materials based on pyrene, porphyrin, and zinc-porphyrin cores connected <i>via</i> diacetylenic linkers. Their electronic structures, investigated at the density functional theory global-hybrid level, are indicative of valence and conduction bands that have large widths, ranging between 1 and 2 eV. Using a molecular approach to derive the electronic couplings between adjacent core units and the electron-vibration couplings, the three π-conjugated 2D COFs are predicted to have ambipolar charge-transport characteristics with electron and hole mobilities in the range of 65-95 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup>. Such predicted values rank these 2D COFs among the highest-mobility organic semiconductors. In addition, we have synthesized the zinc-porphyrin based 2D COF and carried out structural characterization via powder X-ray diffraction and surface area analysis, which demonstrates the feasability of these electroactive networks.</p>

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