Hydrogen-bonded Supramolecular π-Functional Materials

González‐Rodríguez, David; Schenning, Albertus P. H. J.

doi:10.1021/cm101817h

Cited by 406 publications

(240 citation statements)

References 240 publications

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“…[1][2][3][4] NCIs mainly arise from long-range electron correlation effects, [5][6] which are particularly challenging and, thus, an appropriate theoretical description of these weak but important interaction forces requires highly correlated wave function methods. 7 Coupled-cluster theory with singles, doubles, and perturbatively connected triple excitations [CCSD(T)] has become the "gold-standard" method to accurately deal with these interactions in molecular systems.…”

Section: Introductionmentioning

confidence: 99%

“…Density functional theory (DFT), which is possibly by far the most widely used theory for electronic structure calculations, has a more reasonable computational cost ranging from O(N 3 ) to O(N 5 ). Unfortunately, standard density functionals (DFs) are unable to fully capture the longrange electron correlation phenomenon responsible for NCIs, [10][11][12] and thus specific corrections need to be incorporated to make DFs as accurate as possible.…”

Section: Introductionmentioning

confidence: 99%

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Nonlocal van der Waals Approach Merged with Double-Hybrid Density Functionals: Toward the Accurate Treatment of Noncovalent Interactions

Aragó

Ortı́

Sancho‐García

2013

J. Chem. Theory Comput.

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Noncovalent interactions drive the self-assembly of weakly interacting molecular systems to form supramolecular aggregates, which play a major role in nanotechnology and bichemistry. In this work, we present a thorough assessment of the performance of different double-hybrid density functionals (PBE0-DH-NL, revPBE0-DH-NL, B2PLYP-NL, and TPSS0-DH-NL), as well as their parents hybrid and (meta)GGA functionals, in combination with the most modern version of the nonlocal (NL) van der Waals correction. It is shown that this nonlocal correction can be successfully coupled with double-hybrid density functionals thanks to the short-range attenuation parameter b, which has been optimized against reference interaction energies of 2 benchmarking molecular complexes (S22 and S66 databases). Among all the double-hybrid functionals evaluated, revPBE0-DH-NL and B2PLYP-NL behave remarkably accurate with mean unsigned errors (MUE) as small as 0.20 kcal/mol for the training sets and in the 0.24-0.42 kcal/mol range for an independent database (NCCE31). They can be thus seen as appropriate functionals to use in a broad number of applications where noncovalent interactions play an important role. We note in passing that hybrid revPBE0-NL represents an excellent compromise between accuracy (MUE of 0.16 kcal/mol) and computational cost. Overall, the nonlocal van der Waals approach combined with last-generation density functionals is confirmed as an accurate and affordable computational tool for the modeling of weakly-bonded molecular systems.3

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nonlocal van der Waals Approach Merged with Double-Hybrid Density Functionals: Toward the Accurate Treatment of Noncovalent Interactions

Aragó

Ortı́

Sancho‐García

2013

J. Chem. Theory Comput.

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“…[2][3][4] Among the different non-covalent interactions employed to build self-assembled complexes and nanostructures, hydrogen-bonding plays a central role both in artificial and biological systems. [5][6][7][8] Hydrogen-bonds are established when a donor moiety with an available acidic hydrogen atom interacts with an acceptor unit bearing available non-bonding electron lone pairs. This interaction is as a result highly selective and directional, and its strength can be tuned as a function of the chemical nature of the hydrogen-bonding donor and acceptor functions, as well as on their number and sequence in a particular molecular fragment.…”

Section: Introductionmentioning

confidence: 99%

“…[9][10][11][12][13][14] These units are indeed treated as "supramolecular directors", able to bring together specific molecular components in a geometrically defined arrangement in order to obtain the target nanosized assemblies, where in many cases hydrogen-bonding interactions cooperate with additional weak non-covalent forces (like  stacking, ionic or solvophobic interactions). 7,8,[16][17][18]21 Here, we report the synthesis of a series of lipophilic nucleosides comprising natural and non-natural nucleobases that are -conjugated to a short oligophenylene-ethynylene fragment ( Figure 1). Guanosine (G), isoguanosine, (iG) and 2,6-diaminopurine or 2-aminoadenosine (DAP) (A) were employed as purine bases and cytidine (C), isocytosine (iC) and uridine (U) as complementary pyrimidine heterocycles.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and complementary self-association of novel lipophilic π-conjugated nucleoside oligomers

et al. 2015

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Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in: A series of lipophilic nucleosides comprising natural and non-natural bases that are -conjugated to a short oligophenylene-ethynylene fragment has been synthesized. These bases comprise guanosine, isoguanosine, 2-aminoadenosine as purine heterocycles, and cytidine, isocytosine and uridine as complementary pyrimidine bases. The hydrogen-bonding dimerization and association processes between complementary bases were as well studied by 1 H NMR and absorption spectroscopies in order to obtain the relevant association constants.

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“…[1][2][3][4][5][6][7] Many crystalline and mesophase polymers have been developed in order to achieve supramolecular ordering of functional groups and/or the polymer backbone.…”

mentioning

confidence: 99%

Layer-structured Metallopolymers with Pendant Carbazole Groups

Choi

Lee²,

Kwon³

2012

Bulletin of the Korean Chemical Society

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Organic polymers with spatially ordered functional groups often exhibit enhanced physical properties compared to amorphous polymers with randomly orientated functional groups.1-7 Many crystalline and mesophase polymers have been developed in order to achieve supramolecular ordering of functional groups and/or the polymer backbone.1-7 For example, a wholly aromatic polyester consisting of a rigid poly(p-phenylene terephthalate) (PPT) backbone based on 2,5-disubstituted terephthalic acid and large-sized holetransporting groups exhibited either layered or nematic-like mesophase structure.7-10 The spatial ordering in the mesophase structure has shown excellent photorefractive responses for transmission and reflection grating geometries. 7-10We have recently synthesized series of one-dimensional (1D) and three-dimensional (3D) coordinated metallopolymers 11,12 by using a nonconventional polymerization method, the solvothermal reaction.13-15 The metallopolymers synthesized with zinc salts and 2,5-disubstituted terephthalic acid bearing flexible side chains exhibited either layered mesophase or isoreticular metal-organic framework (IRMOF) structures, 16 depending on the lengths and flexibilities of the side chains.13-15 However, in metallopolymers synthesized using the solvothermal reaction, the influences of large-sized pendant groups on their mesophase behavior and resulting physical properties have not been fully understood yet.Here we report on the design and synthesis of a series of mesophase metallopolymers with pendant groups. New metallopolymers were synthesized using the solvothermal reaction of zinc nitrate and 2,5-disubstituted terephthalic acids bearing oxyalkyl-9H-carbazole groups with various length of alkyl spacers (see Figure 1(a)). Despite the large size of the pendant carbazole groups, the metallopolymers exhibit layer-structured mesophase, and their layer distances and glass transition temperatures vary systematically with the length of the oxyalkyl spacers. The layer distances of the metallopolymers with oxyalkyl-9H-carbazole groups are larger than those of previously reported wholly aromatic polyesters with identical oxyalkyl-9H-carbazole groups.In order to investigate the influence of large-sized pendant groups on the mesophase characteristics in metallopolymers, a carbazole (CZ) group was introduced into the terephthalic acid. The chemical structure of the organic linkers, CZmacid bearing oxyalkyl-9H-carbazole groups, is shown in Figure 1(a). The carbazole groups are linked by oxyalkyl spacers (m = 6, 8, 9, 10, 11, and 12), where m is the number of methylene units in the flexible oxyalkyl chains. New ZnCZm metallopolymers were synthesized using a solvothermal reaction of zinc nitrate and CZm-acid. In the newly synthesized ZnCZm metallopolymers, the coordination between zinc metal and carboxylate groups (see Figure 1(b)) was determined using thermogravimetric analysis (TGA) from the amount of ZnO ash remaining after combustion at high temperature (> 500 °C) under a mixture of O 2 and air. In infra...

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Hydrogen-bonded Supramolecular π-Functional Materials

Abstract: Recent developments in the area of H-bonded supramolecular assemblies of π-conjugated systems, that is, oligomers and polymers, are described. The state-of-the-art summary of the recent developments in the design of discrete systems and functional materials is presented.

Cited by 406 publications

References 240 publications

Nonlocal van der Waals Approach Merged with Double-Hybrid Density Functionals: Toward the Accurate Treatment of Noncovalent Interactions

Nonlocal van der Waals Approach Merged with Double-Hybrid Density Functionals: Toward the Accurate Treatment of Noncovalent Interactions

Synthesis and complementary self-association of novel lipophilic π-conjugated nucleoside oligomers

Layer-structured Metallopolymers with Pendant Carbazole Groups

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