Structural study and electrical conductivity of salts based on functionalized TTF containing peripheral selenium atoms

Kaboub, Lakhémici; Legros, Jean-Pierre; Donnadieu, Bruno; Gouasmia, Abdelkrim; Boudiba, Louiza; Fabre, Jean‐Marc

doi:10.1039/b308514g

Cited by 9 publications

(7 citation statements)

References 25 publications

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“…Fx and Qy correspond to derivatives of F and Q considered herein. F, F1‐F14 correspond to F derivatives co‐crystallized with Q, and Q, Q1, and Q2 correspond to Q derivatives co‐crystallized with F. F⋅Q, F1⋅Q, F2⋅Q, F3⋅Q, F4⋅Q, F5⋅Q, F6⋅Q, and F⋅Q1 exhibit Class 1 packing. F6a⋅Q, F7⋅Q, F8⋅Q, F9⋅Q, F10⋅Q, F11⋅Q, and F⋅Q2 show Class 2 packing.…”

Section: Resultsmentioning

confidence: 99%

“…Hirshfelds urface analysis [52] and 2D fingerprint plot analysis [65] were performed to investigate the perturbationsi ni ntermolecularc ontactso f Qc aused by variouss ubstituents on the Fu nit for the co-crystals Fx·Q (Figure2;T able S1 and Figure S1, Supporting Information). In co-crystals F·Qy,t he percentage of contacts were inspectedf or the Fu nit by altering Qy.A ll the Class 1c o-crystals of Fx·Q exhibited higher C···C, CÀH···C, C···N, H···H, andC ÀH···N contacts.X -ray crystal structure analysis of the co-crystals revealed the qualitative significance of intermolecularC ···C (all carbonsa re sp 2 -hybridized if not mentioned otherwise), C···C sp (in F·Q, F1·Q-F4·Q), andC sp 3ÀH···C (in F·Q1) interactions in driv-Scheme1.Scheme of search in CSD for co-crystals containingFand Qasc ore.F xa nd Qy correspond to derivatives of Fa nd Qc onsidered herein.F ,F 1-F14 correspond to Fd erivatives co-crystallized with Q, and Q, Q1, and Q2 correspond to Qderivatives co-crystallized with F. F·Q, [67] F1·Q, [68] F2·Q, [69] F3·Q, [70] F4·Q, [71] F5·Q, [72] F6·Q, [73] and F·Q1 [74] exhibitC lass 1p acking. F6a·Q, [75] F7·Q, [76] F8·Q, [77] F9·Q, [76] F10·Q, [76] F11·Q, [76] and F·Q2 [78] show Class 2p acking.C lass 3a type includes F12·Q [79] and F13·Q, [80] whereas F14·Q [81] displays Class3bp acking.…”

Section: Resultsmentioning

confidence: 99%

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Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Niyas

Vijay

Hariharan

2018

Chemistry A European J

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Among the various donor-acceptor (D-A) charge-transfer co-crystals investigated in the past few decades, tetrathiafulvalene-tetracyanoquinodimethane (F⋅Q, popularly known as TTF⋅TCNQ)-based co-crystals have fascinated materials chemists owing to their exceptional conducting and magnetic properties that arise from the packing in crystal structures. Here, crystallographic information files of eighteen F⋅Q-based co-crystals are extracted from the Cambridge Structural Database (CSD) and classified into Class 1 (D-on-D and A-on-A segregated stacks; F⋅Q, F1⋅Q-F6⋅Q, and F⋅Q1), Class 2 (-A-D-A-D-A-D- mixed stacks; F6a⋅Q-F11⋅Q and F⋅Q2), and Class 3 [-A-D-A-A-D-A-; Class 3a (F12⋅Q and F13⋅Q) and -D-D-A-A-; Class 3b (F14⋅Q)] systems according to their packing modes. Hirshfeld surface analysis, PIXEL energy calculations, and quantum theory of atoms in molecules (QTAIM) analysis are performed on the selected multicomponent charge-transfer crystals for the first time, in an attempt to explore the driving forces that give rise to different classes of 3 D crystal packing, which in turn mandates the expedient electronic properties exhibited by the investigated co-crystals. PIXEL calculations reveal that the dispersion energy component makes the maximum contribution to the total lattice energy for most of the F⋅Q-based co-crystals under study. Although the Q-on-Q dimer is the energetically most favored dimer in F⋅Q, the substituents on F capable of forming hydrogen-bonding, C⋅⋅⋅S, and other weak intermolecular interactions result in the greater stability of the F-on-F dimer for F1⋅Q-F6⋅Q (except F2⋅Q). The C⋅⋅⋅S, C ⋅⋅⋅S, S⋅⋅⋅N, and π⋅⋅⋅π interaction-driven D-on-A dimer is found to be the most stable dimer of all the Class 2 co-crystals. Band structure and density-of-state calculations of the representative co-crystals in each class indicate different electronic structures according to the packing arrangement. F⋅Q and F6⋅Q with a high interaction of electronic orbitals between D-on-D and A-on-A in segregated stacks are found to be metal-like (bandgap, E =0.003 eV) and metallic (overlapping bands in the Fermi level), respectively, whereas the polymorph of F6⋅Q belonging to Class 2 (F6a⋅Q) displays a semiconductor-type band structure (E =0.053 eV). F12⋅Q of Class 3a exhibits a metal-like band structure (E =0.001 eV). The fine tuning of chromophores with diverse functional substituents capable of triggering weak intermolecular interactions that give rise to the desired packing and charge-transfer properties has the potential to open floodgates of opportunity for research in the chemistry of materials and fabrication of efficient electronic devices.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Niyas

Vijay

Hariharan

2018

Chemistry A European J

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“…We have discussed the origin of the semiconducting behavior of some of the TTF derivatives and indicated that the semiconducting salts exhibited a charge transfer band at higher energy, suggesting stronger coulombic repulsions. The possibility of producing new cation-radical salts in these series and the X-ray structural details [12], are under investigation.…”

Section: Discussionmentioning

confidence: 99%

“…They were found to be versatile starting new donors for the synthesis of new organic materials. Recently, and proceeding from accessible conducting organic materials, we synthesized a series of TTF derivatives containing peripheral selenium atoms and demonstrated their ability to form charge transfer complexes and radical cation salts [11,12]. Within the framework of our interest in organic materials we now describe in this paper the synthesis and properties of some new asymmetrical donors containing acetoxyphenyl and hydroxyphenyl groups.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of Novel Unsymmetrical Donor Molecules Containing p-Acetoxy- or p-Hydroxyphenyl Units

2006

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Abstract:We report the synthesis and properties of eight new tetrathiafulvalene (TTF) derivatives containing two different functionalities, prepared with the aim of obtaining stable organic materials. The four acetoxyphenyl-and four hydroxyphenyl TTFs were synthesized via Wittig-type condensations. The electrochemical properties of these redox-active molecules were studied by cyclic voltammetry. Charge transfer complexes with tetracyanoquinodimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials. The UV-VIS and IR spectra of the TCNQ salts were recorded and used to characterize and estimate the degree of charge transfer of these complexes.

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“…3,4 To achieve this purpose, numerous tracks were developed, passing by the preliminary modification of the skeleton of the tetrathiafulvalene (TTF). Among these modifications are the multiplication of heteroatoms [5][6][7][8][9] within the donor, and the introduction of the combined systems more widened to limit the coulomb repulsion and strengthen the coverings of orbital inter-and intrachains in the resultant material. [10][11][12][13] In these optics, we focused on the synthesis and solution redox properties at a new series of π -donors, in which 1,3-dithiole ring frameworks are attached to the periphery of TTF (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

New π-Extended Donors: Synthesis, Characterization, Electrochemical and Electrical Conductivity Studies

Zitouni

Gouasmia

Bouguessa

et al. 2011

Phosphorus, Sulfur, and Silicon and the Related Elements

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A new series of tetrathiafulvalene (TTF) molecules with extended π -system was prepared by using a Wittig reaction to generate the TTF key. The process of deprotection-alkylation of thiolates provided access to a wide variety of molecules. The study of their reducing power was carried out by cyclic voltammetry. Charge transfer complexes have also been chemically prepared by using TCNQ as an electron acceptor; the electrical conductivity of their compressed powders shows insulator behavior. The IR spectra of the TCNQ salts were recorded and used to characterize and estimate the degree of charge transfer of these complexes.

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Structural study and electrical conductivity of salts based on functionalized TTF containing peripheral selenium atoms

Cited by 9 publications

References 25 publications

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Structure‐Packing‐Property Correlation of Self‐Sorted Versus Interdigitated Assembly in TTF⋅TCNQ‐Based Charge‐Transport Materials

Synthesis and Properties of Novel Unsymmetrical Donor Molecules Containing p-Acetoxy- or p-Hydroxyphenyl Units

New π-Extended Donors: Synthesis, Characterization, Electrochemical and Electrical Conductivity Studies

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