Mixed Stack Organic Semiconductors: The Anomalous Case of the BTBT-TCNQF<sub><i>x</i></sub> Series

Castagnetti, Nicola; Girlando, Alberto; Masino, Matteo; Rizzoli, Corrado; Rovira, Concepció

doi:10.1021/acs.cgd.7b00852

Cited by 18 publications

(29 citation statements)

References 25 publications

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“…These crystals may exhibit dominant D-D and/or A-A interstack repulsions along directions perpendicular to the stack. Based on the extensive number of investigated systems, we advance the plausible hypothesis that largely positive c values imply a lattice contraction upon decreasing temperature, whereas strongly negative values point to a lattice instability [43].…”

Section: Discussionmentioning

confidence: 72%

“…Their difference reflects the inter-stack interactions, and positive c point to the presence of dominant attractive inter-stack interactions, larger than the intra-stack one. This is the case for all the TMB series, but in other cases negative c have been found [24,43], typically corresponding to crystals with one DA pair per unit cell. These crystals may exhibit dominant D-D and/or A-A interstack repulsions along directions perpendicular to the stack.…”

Section: Discussionmentioning

confidence: 81%

“…Table III), again a likely consequence of the inclination of the molecules with respect to stack axis. These differences in t and in M are in any case not sufficient to affect the increase in ρ with the decrease of z, as it happens instead in the BTBT-TCNQF x series [43].…”

Section: Discussionmentioning

confidence: 92%

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Mixed stack charge transfer crystals: Crossing the neutral-ionic borderline by chemical substitution

Castagnetti

Masino

Rizzoli

et al. 2018

Phys. Rev. Materials

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We report extensive structural and spectroscopic characterization of four mixed stack chargetransfer (ms-CT) crystals formed by the electron donor 3,3',5,5'-tetramethylbenzidine (TMB) with Chloranil (CA), Bromanil (BA), 2,5-difluoro-tetracyanoquinodimethane (TCNQF2) and tetrafluorotetracyanoquinodimethane (TCNQF4). Together with the separately studied TMB-TCNQ [Phys. Rev. B 95, 024101 (2017)] the TMB-acceptor series span a wide range of degree of CT, from about 0.14 to 0.91, crossing the neutral-ionic interface, yet retaining similar packing and donor-acceptor CT integrals. First principle calculations of key phenomenological parameters allows us to get insight into the factors determining the degree of CT and other relevant physical properties.

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Section: Discussionmentioning

confidence: 72%

Section: Discussionmentioning

confidence: 81%

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Mixed stack charge transfer crystals: Crossing the neutral-ionic borderline by chemical substitution

Castagnetti

Masino

Rizzoli

et al. 2018

Phys. Rev. Materials

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“…Cocrystals of donor and acceptor semiconductors have to face a twofold requirement. On one hand, their shape must be complementary, and on the other hand, their orbital symmetry must match for efficient charge transfer from the donor to the acceptor . The number of potential donor–acceptor combinations is extremely large, especially when considering 1:2, 1:3, or 2:1, 3:1 instead of simply 1:1.…”

Section: Charge Transportmentioning

confidence: 99%

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

et al. 2020

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The field of organic electronics has been prolific in the last couple of years, leading to the design and synthesis of several molecular semiconductors presenting a mobility in excess of 10 cm2 V−1 s−1. However, it is also started to recently falter, as a result of doubtful mobility extractions and reduced industrial interest. This critical review addresses the community of chemists and materials scientists to share with it a critical analysis of the best performing molecular semiconductors and of the inherent charge transport physics that takes place in them. The goal is to inspire chemists and materials scientists and to give them hope that the field of molecular semiconductors for logic operations is not engaged into a dead end. To the contrary, it offers plenty of research opportunities in materials chemistry.

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“…[1] Recent years have witnessed a surge in the literature on the syntheses and theoretical predictions of various classes of organic charge-transfer salts andc o-crystalsi nt he wake of the development of advanced functional materials. [2][3][4][5] Segregated stacking of D-Ac o-crystals provides profitablea mbipolar electricalc onductivity [6][7][8] along the stacking direction,w hereas mixed stacking crystalline structural modes [9,10] possess the ability to form pairwise molecular dimers and cause high ferroelectric behavior [11,12] through neutral-ionic phase transition [13] or spin-Peierls phaset ransition mechanisms. [12][13][14] Although rare, various D-A packing modes with different stoichiometric ratios have also been observed in the literature, but have not been studied as extensively as 1:1 stoichiometric segregated or mixed stacking D-A co-crystals.…”

Section: Introductionmentioning

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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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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Mixed Stack Organic Semiconductors: The Anomalous Case of the BTBT-TCNQF_x Series

Cited by 18 publications

References 25 publications

Mixed stack charge transfer crystals: Crossing the neutral-ionic borderline by chemical substitution

Mixed stack charge transfer crystals: Crossing the neutral-ionic borderline by chemical substitution

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

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

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Mixed Stack Organic Semiconductors: The Anomalous Case of the BTBT-TCNQFx Series

Cited by 18 publications

References 25 publications

Mixed stack charge transfer crystals: Crossing the neutral-ionic borderline by chemical substitution

Mixed stack charge transfer crystals: Crossing the neutral-ionic borderline by chemical substitution

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

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

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Product

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Mixed Stack Organic Semiconductors: The Anomalous Case of the BTBT-TCNQF_x Series