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Review
. 2018 Jan 7;23(1):118.
doi: 10.3390/molecules23010118.

Quantum-Chemical Insights Into the Self-Assembly of Carbon-Based Supramolecular Complexes

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Free PMC article
Review

Quantum-Chemical Insights Into the Self-Assembly of Carbon-Based Supramolecular Complexes

Joaquín Calbo et al. Molecules. .
Free PMC article

Abstract

Understanding how molecular systems self-assemble to form well-organized superstructures governed by noncovalent interactions is essential in the field of supramolecular chemistry. In the nanoscience context, the self-assembly of different carbon-based nanoforms (fullerenes, carbon nanotubes and graphene) with, in general, electron-donor molecular systems, has received increasing attention as a means of generating potential candidates for technological applications. In these carbon-based systems, a deep characterization of the supramolecular organization is crucial to establish an intimate relation between supramolecular structure and functionality. Detailed structural information on the self-assembly of these carbon-based nanoforms is however not always accessible from experimental techniques. In this regard, quantum chemistry has demonstrated to be key to gain a deep insight into the supramolecular organization of molecular systems of high interest. In this review, we intend to highlight the fundamental role that quantum-chemical calculations can play to understand the supramolecular self-assembly of carbon-based nanoforms through a limited selection of supramolecular assemblies involving fullerene, fullerene fragments, nanotubes and graphene with several electron-rich π-conjugated systems.

Keywords: carbon-based supramolecular assemblies; noncovalent interactions; quantum chemistry.

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Selected examples of supramolecular assemblies involving fullerene (a), nanotubes (b) and graphene (c) with different π-conjugated electron-donors. The carbon atoms of the electron-acceptor carbon-based systems have been highlighted in red whereas the carbon atoms of the electron-donor systems are colored in green. Sulfur, oxygen and hydrogen atoms in the electron-donor systems are colored in yellow, red and white, respectively.
Figure 2
Figure 2
Chemical structure of TTF (a) and exTTF (b). The curved shape of exTTF is also represented (c). Sulfur, carbon and hydrogen atoms are colored in yellow, green and white, respectively. Chemical structures of the supramolecular complexes MTWC60 (d) and PTWC60 (e) are also shown.
Figure 3
Figure 3
Complexes obtained from exTTF-based 16 and C60. Reproduced from Reference [84] with permission from the Royal Society of Chemistry.
Figure 4
Figure 4
Minimum-energy embraced (a) and non-embraced (b) conformations calculated at the PM7 level for the 2•C60 complex. The electron-acceptor C60 is colored in red whereas the sulfur, carbon, oxygen and hydrogen atoms in the electron-donor system are colored in yellow, green, red and white, respectively.
Figure 5
Figure 5
B97-D/cc-pVDZ minimum-energy geometries calculated for the exTTF•C60 and 16•C60 complexes. The electron-acceptor C60 is colored in red whereas the sulfur, carbon, oxygen and hydrogen atoms in the electron-donor system are colored in yellow, green, red and white, respectively.
Figure 6
Figure 6
Side view of the B97-D/cc-pVDZ-optimized geometries calculated for complexes 2•C60 (a) and 5•C60 (b) showing the different spatial arrangement of the crown and aza-crown ethers, respectively, along the C60 guest. The electron-acceptor C60 is colored in red whereas the sulfur, carbon, oxygen and hydrogen atoms in the electron-donor system are colored in yellow, green, red and white, respectively.
Figure 7
Figure 7
Chemical structure of the truxene and truxTTF compounds.
Figure 8
Figure 8
Minimum-energy structures of the truxTTF•C60 complex calculated at the MPWB1K/6-31G** level. Top and side view of structures CC (a) and CS (b) are given. The electron-acceptor C60 is colored in red whereas the sulfur, carbon and hydrogen atoms in the electron-donor system are colored in yellow, green and white, respectively.
Figure 9
Figure 9
Chemical structure of the methano[60] fullerene guest 7 (Left), the metalloporphyrin host 8-M (Center), and the host–guest supramolecular complex 8-M•7 (Right). M refers to either 2H, Co., Ni, Cu or Zn.
Figure 10
Figure 10
Minimum-energy geometries calculated for the 8-Cu•7 complex at the PM7 level. Side (Left) and front (Right) views are displayed. The different types of intermolecular contacts are denoted with labels a–d. Only relevant hydrogen atoms are displayed for clarity. Except for C60 carbon atoms depicted in grey, the following color code is used: carbon in green, nitrogen in blue, oxygen in red and hydrogen in white.
Figure 11
Figure 11
Porphyrin•C2H4 model (MP•C2H4) used to understand the nature of the interaction between the porphyrin host 8 and the fullerene derivative guest 7. Except for the ethylene carbon atoms depicted in red, the following color code is used: carbon in green, nitrogen in blue and hydrogen in white.
Figure 12
Figure 12
Chemical structure of the ditopic porphyrin-based hosts 9 and 10.
Figure 13
Figure 13
Chemical structure (Left) and minimum-energy geometry calculated at the B97-D3/(6-31G**+LANL2DZ) level (Right) of the supramolecular assembly of ditopic host 9 with one and two molecules of guest 7. Except for C60 carbon atoms depicted in grey, the following color code is used: carbon in green, nitrogen in blue, oxygen in red and hydrogen in white. Adapted with permission from [90]. Copyright 2014 American Chemical Society.
Figure 14
Figure 14
Chemical structure (left) and minimum-energy geometry calculated at the B97-D3/(6-31G**+LANL2DZ) level (right) for the supramolecular assembly of ditopic host 10 with one and two molecules of guest 7. Except for C60 carbon atoms depicted in grey, the following color code is used: carbon in green, nitrogen in blue, oxygen in red and hydrogen in white. Adapted with permission from [90]. Copyright 2014 American Chemical Society.
Figure 15
Figure 15
Chemical structure of the hemifullerene C30H12 buckybowl (a); Structure of the dimers formed by C30H12 (carbon atoms in red) in its trigonal (b) and orthorhombic (c) crystal polymorphs, respectively; (d) Dimers formed by truxTTF in the crystal. For C30H12, the carbon atoms are depicted in red and hydrogen atoms in white. For truxTTF, the sulfur, carbon and hydrogen atoms are colored in yellow, green and white, respectively.
Figure 16
Figure 16
Minimum-energy structures (A14) computed for the truxTTF•C30H12 heterodimer at the revPBE0-D3/cc-pVTZ level. For C30H12, the carbon and hydrogen atoms are depicted in red and white, respectively. For truxTTF, the sulfur, carbon and hydrogen atoms are colored in yellow, green and white, respectively.
Figure 17
Figure 17
Selected intermolecular distances computed for structures A1A4 at the revPBE0-D3/cc-pVTZ level. For C30H12, the carbon and hydrogen atoms are depicted in red and white, respectively. For truxTTF, the sulfur, carbon and hydrogen atoms are colored in yellow, green and white, respectively. Adapted with permission from [18]. Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA.
Figure 17
Figure 17
Selected intermolecular distances computed for structures A1A4 at the revPBE0-D3/cc-pVTZ level. For C30H12, the carbon and hydrogen atoms are depicted in red and white, respectively. For truxTTF, the sulfur, carbon and hydrogen atoms are colored in yellow, green and white, respectively. Adapted with permission from [18]. Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA.
Figure 18
Figure 18
(a) Experimental UV–Vis spectra, as obtained during the titration of truxTTF (1.7 × 10−4 M) with C30H12 (0.8 × 10−3 M) in CHCl3 at room temperature; (b) TD-DFT simulation of the absorption spectrum of truxTTF as the ratio of truxTTF•C30H12 increases from 0 to 100% (B3LYP/cc-pVDZ calculations including CHCl3 as solvent for structure A4). Adapted with permission from [18]. Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA.
Figure 19
Figure 19
Isovalue contours (±0.03 a.u.) and energies calculated for the HOMOs and LUMOs of structure A4 at the revPBE0-D3/cc-pVTZ level. H and L denote HOMO and LUMO, respectively. Adapted with permission from [18]. Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA.
Figure 20
Figure 20
Chemical structure of corannulene-based C32H12 and C38H14 buckybowls. The corannulene skeleton is highlighted in red.
Figure 21
Figure 21
Minimum-energy structures and computed at the revPBE0-D3/cc-pVTZ level for the most stable conformations of the heterodimers formed by the C32H12 (B14) and C38H14 (C16) fullerene fragments with truxTTF (truxTT•C32H12 and truxTT•C38H14). Except for the carbon atoms of the C32H12 and C38H14 buckybowls depicted in red, the following color code is used: carbon in green, sulfur in yellow and hydrogen in white. Adapted with permission from Reference [19]. Copyright 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Figure 22
Figure 22
Chemical structure of a SWNT model and the hosts used to supramolecularly interact with SWNTs and test the experimental association constant protocol.
Figure 23
Figure 23
Minimum-energy geometries of parallel 11•SWNT assemblies and the perpendicular 11•C200H20 calculated at the PBE0-D3/6-31G** level from a semi-rigid optimization with fixed intramolecular parameters (see the original Reference [117] for further details). Carbon atoms of SWNTs are highlighted in red whereas the carbon atoms of pyrene are in green. Hydrogen atoms are depicted in white. Reproduced from Reference [117] with permission from the Royal Society of Chemistry.
Figure 24
Figure 24
Minimum-energy geometry for the supramolecular assemblies formed by hosts 1115 vs. SWNTs calculated at the PBE0-D3/6-31G** level of theory. Reproduced from [117] with permission from the Royal Society of Chemistry.
Figure 25
Figure 25
Side view of the supramolecular complex formed by 11 and two types of SWNTs. Carbon atoms of SWNTs are highlighted in red whereas the carbon atoms of pyrene are in green. Hydrogen atoms are depicted in white. Reproduced from [117] with permission from the Royal Society of Chemistry.
Figure 26
Figure 26
Plot of lnKa vs. −Ebind, comparing the experimental and calculated data.
Figure 27
Figure 27
Minimum-energy structures computed for the exTTF-graphene models (G1G5) at the revPBE0-D3/cc-pVDZ level. Carbon atoms of exTTF are depicted in green, sulfur in yellow and hydrogen in white. Carbon atoms of the graphene sheet are depicted in red and hydrogen atoms have been omitted for clarity. Adapted with permission from [120]. Copyright 2013 WILEY-VCH Verlag GmbH & Co. KGaA.
Figure 28
Figure 28
(a) Top and side views of the minimum-energy geometry computed for anthracene-graphene (G6) at the revPBE0-D3/cc-pVDZ level. The intermolecular interacting regions of anthracene and graphene are colored in red; (b) Magnification of the interacting region emphasizing the most representative intermolecular distances collected in the table. Adapted with permission from [120]. Copyright 2013 WILEY-VCH Verlag GmbH & Co. KGaA.

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