CH…S and S…S: Two major forces in organic conductors

Novoa, Juan J.; Rovira, Meritxell; Rovira, Concepció; Veciana, Jaume; Tarrés, Judit

doi:10.1002/adma.19950070230

Cited by 129 publications

(90 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…On the other hand, the packing of the neutral crystals is a compromise between the S´´´S interactions and the competing CÀH´´´S ones. [14] Notice also that both d SÀS distributions are similar to those found by Gavezzotti et al [7d] in a much broader subset of crystals. Therefore, the S´´´S interactions in TTF-based crystals can be modeled by the Figure 2, within the TTF-based neutral crystals.…”

Section: Resultssupporting

confidence: 81%

Strength and Directionality of the S⋅⋅⋅S Intermolecular Interactions Present in TTF-Based Molecular Crystals. A Combined Statistical and Ab Initio Study

Rovira¹,

Novoa²

1999

Chem. Eur. J.

Self Cite

View full text Add to dashboard Cite

Abstract:The strength and directionality of the S´´´S interactions have been evaluated by combining the results from the statistical analysis of neutral and charge-transfer molecular crystals of the tetrathiafulvalene (TTF) family with those from Mùller ± Plesset (MP2) calculations on model systems. The model systems have been designed to represent the environment of the S´´´S interactions in these crystals. Our statistical analysis of the geometrical distribution of the S´´´S contacts in these crystals suggests that they are attractive and that there is a maximum probability for collinear S´´´S orientations. Small differences are found between the neutral and charge-transfer distributions. MP2 computations on the H 2 S dimer and functionalized XYS dimers oriented to present short S´´´S contacts show that the S´´´S interactions are attractive and quite anisotropic. Their strength depends significatively on the X and Y functional groups and can be of the order of À 1.5 kcal mol À1 for the p ± p interactions between the five-membered rings of the TTF molecule. Consequently, S´´´S interactions should contribute significantly to the cohesive energy of TTF-based crystals.

show abstract

Section: Resultssupporting

confidence: 81%

Strength and Directionality of the S⋅⋅⋅S Intermolecular Interactions Present in TTF-Based Molecular Crystals. A Combined Statistical and Ab Initio Study

Rovira¹,

Novoa²

1999

Chem. Eur. J.

Self Cite

View full text Add to dashboard Cite

show abstract

“…In contrast to the octahedrally coordinated Na atoms (two N and four O atoms) in salt 1, the lithium ions in 2 are À unit exhibits two Se¥¥¥HÀC contacts (Se1¥¥¥H4ÀC4 3.015 ä, q = 1558) [20] between the H atoms of the pds ligand and the closest Se atoms of the perpendicular complexes of the neighboring stacks. At the same time each complex shows two strong N¥¥¥H À OH hydrogen bonds (N2¥¥¥H À O 1.948 ä, q = 1768) [21] between the uncoordinated N atom and the H atom of a water molecule that belongs to the coordination sphere of the Li atom.…”

Section: Resultsmentioning

confidence: 95%

“…Thus, one-dimensional chains of alternating Na ions and two water molecules along a are formed between the parallel stacks of [Cu III (pdt) 2 ] À complexes (Figure 8). À unit has four short S¥¥¥HÀC contacts (S1¥¥¥H3ÀC3 2.873 ä, q = 1638; S2'¥¥¥H4ÀC4 2.985 ä, q = 1298) [20] between the H atoms of the pdt ligand and the closest S atoms of the perpendicular complexes of the neighboring stacks. At the same time each complex shows two moderately strong N¥¥¥HÀOH hydrogen bonds (N2¥¥¥HÀO 2.142 ä, q = 1468) [21] between the uncoordinated N atom and the H atom of a water molecule that belongs to the coordination sphere of the Na atom.…”

Section: Resultsmentioning

confidence: 99%

Novel Cu^III Bis‐1,2‐dichalcogenene Complexes with Tunable 3D Framework through Alkaline Cation Coordination: A Structural and Theoretical Study

Ribas

Dias

Morgado

et al. 2004

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The deprotonated form of the ligands pyrazine-2,3-diselenol (pds) and pyrazine-2,3-dithiol (pdt) react with Cu(ClO(4))(2).6 H(2)O to form different Cu(III) complexes Na[Cu(III)(pds)(2)].2 H(2)O (1), Li[Cu(III)(pds)(2)].3 H(2)O (2), and Na[Cu(III)(pdt)(2)].2 H(2)O (4) depending on the countercation compound used as deprotonating agent (NaOH, LiOH). Two other Cu(III) complexes were obtained by replacement of the alkali metal cations with tetrabutylammonium (TBA(+)), namely, TBA[Cu(III)(pds)(2)] (3), and TBA[Cu(III)(pdt)(2)] (5). All complexes were characterized by (1)H and (13)C NMR and IR spectroscopy, electronic absorption, elemental analysis, cyclic voltammetry (CV), and X-ray crystallography. Electrical conductivity measurements on single crystals show that these salts exhibit insulating behavior. The crystal structure of these species revealed a lateral coordination capability of the N atoms of the pyrazine ring of both pds and pdt ligands towards the alkali metal ions, which leads to the build up of a net of coordinative bonds, hydrogen bonds, and contacts that result in the final 3D structure. Two parameters control the crystal engineering of the final 3D structures: the nature of the alkali metal countercation and the nature of the chalcogen atom (Se/S), which allow fine-tuning of complex 3D crystal lattice. Density functional calculations were performed on the [Cu(pds)(2)] and [Cu(pdt)(2)] systems to investigate the electronic structure of the complexes and understand their electronic and electrochemical behavior by studying the frontier molecular orbitals. This study also reveals whether the redox processes take place on the ligands or on the metal center, a question under continuous discussion in the literature.

show abstract

“…It was found that besides close S ¥¥¥ S contacts, C À H ¥¥¥ S, C À H ¥¥¥ p and p ± p stacking contribute to the solid-state structures. [30] The examination of the S ¥¥¥ S distances and the resulting configurations of a series of compounds belonging to the type R-S-R' with R,R'=H could be rationalized in terms of electrophilic ± nucleophilic interactions of different sulfur centers, or by considering the corresponding frontier orbitals ( Figure 5). [25,31] In most cases the arrangement of the planes, defined by R, S, and R', was that one R-S-R' unit (say the electrophile) approaches the other R-S-R' unit (the nucleophile), in such a way that both planes are nearly perpendicular to each other ( Figure 5).…”

Section: Van Der Waals Forcesmentioning

confidence: 99%

A World Beyond Hydrogen Bonds?—Chalcogen–Chalcogen Interactions Yielding Tubular Structures

Gleiter

Werz

Rausch

2003

Chemistry A European J

167

120

View full text Add to dashboard Cite

It is shown that tubular structures arise in the solid state through close chalcogen-chalcogen (X...X) contacts. As examples a variety of cyclic systems containing sulfur and selenium centers is presented. Common to all of them are close contacts between the chalcogen centers of neighboring stacks giving rise to a zigzag or ladder-type arrangement. In the case of cyclic systems of ring size 24-33 the resulting tubes are able to include hydrocarbons as guest molecules. For 2,7-ditelluraocta-3,5-diyne (17) the close contacts between the tellurium centers of the acyclic C(2) symmetric building blocks generate a helical arrangement in which n-hexane was included. The favored X...X contacts can be traced back to np(X)-sigma*(X[bond]C) interactions.

show abstract

CH…S and S…S: Two major forces in organic conductors

Cited by 129 publications

References 20 publications

Strength and Directionality of the S⋅⋅⋅S Intermolecular Interactions Present in TTF-Based Molecular Crystals. A Combined Statistical and Ab Initio Study

Strength and Directionality of the S⋅⋅⋅S Intermolecular Interactions Present in TTF-Based Molecular Crystals. A Combined Statistical and Ab Initio Study

Novel Cu^III Bis‐1,2‐dichalcogenene Complexes with Tunable 3D Framework through Alkaline Cation Coordination: A Structural and Theoretical Study

A World Beyond Hydrogen Bonds?—Chalcogen–Chalcogen Interactions Yielding Tubular Structures

Contact Info

Product

Resources

About

CH…S and S…S: Two major forces in organic conductors

Cited by 129 publications

References 20 publications

Strength and Directionality of the S⋅⋅⋅S Intermolecular Interactions Present in TTF-Based Molecular Crystals. A Combined Statistical and Ab Initio Study

Strength and Directionality of the S⋅⋅⋅S Intermolecular Interactions Present in TTF-Based Molecular Crystals. A Combined Statistical and Ab Initio Study

Novel CuIII Bis‐1,2‐dichalcogenene Complexes with Tunable 3D Framework through Alkaline Cation Coordination: A Structural and Theoretical Study

A World Beyond Hydrogen Bonds?—Chalcogen–Chalcogen Interactions Yielding Tubular Structures

Contact Info

Product

Resources

About

Novel Cu^III Bis‐1,2‐dichalcogenene Complexes with Tunable 3D Framework through Alkaline Cation Coordination: A Structural and Theoretical Study