Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Goetz, Katelyn P.; Tsutsumi, Jun; Pookpanratana, Sujitra J.; Chen, Jihua; Corbin, Nathan; Behera, Rakesh K.; Coropceanu, Veaceslav; Richter, Curt A.; Hacker, Christina A.; Hasegawa, Tatsuo; Jurchescu, Oana D.

doi:10.1002/aelm.201600203

Cited by 85 publications

(110 citation statements)

References 65 publications

(118 reference statements)

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“…Powder X‐ray diffraction (XRD) shows an identical diffraction pattern for solution and vapor‐grown cocrystals and confirms the absence of the crystalline phases of the individual components, indicating the effectiveness of gas‐phase growth to grow high‐quality cocrystals . Meanwhile, the source materials of cocrystals can originate from well‐grown cocrystals from solution but not those mixtures of separate donor and acceptor molecules, which effectively improves the yield and quality of cocrystals …”

Section: Rational Design and Controllable Preparation Of Organic Cocrmentioning

confidence: 89%

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

et al. 2019

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materials, [9][10][11][12] which are crystalline singlephase materials composed of two or more different compounds generally in a stoichiometric ratio, [13] providing a platform for unveiling the structure-property relationships at a molecular level. [14] The building blocks are assembled via noncovalent interactions, offering the opportunity to achieve noncovalent synthesis of functional molecules. [15] Compared with the traditional covalent synthesis, cocrystal engineering offers numerous advantages, including: 1) avoiding complicated synthesis procedures, and cocrystal assemblies have been successfully fabricated by the vapor methods and solution-processing methods in a facile and low-cost way; 2) manipulating intermolecular interactions through selecting suitable conformers from a plentiful supply of raw materials, resulting in tunable structures, morphologies, and sizes; 3) achieving rare and multifunctional properties through a collaborative strategy in distinct constituent units, which are difficult to realize for individual components. [16][17][18] Cocrystal engineering began to draw much attention since the exploration of the metal conductive tetrathiafulvalene-7,7,8,8-tetracyanoquinodimethane (TTF-TCNQ) cocrystals in 1973. [19] The peculiar conductivity in organic materials makes it possible for cocrystals to serve as organic electrodes, which can effectively lower the contact resistance and further improve device performance. Encouraged by this, cocrystals can serve as a breakthrough and provide an opportunity to discover novel physicochemical properties, which are far beyond the performance of single materials. In this respect, dielectric response [20] and nonlinear optics [21,22] are also realized through rational design of each component, which is absent in their constitute components. Even more, the bottom-up supramolecular assembly provides the opportunity to equip them with the individual properties of the donor or acceptor to create multifunctional materials. [23] Typically, ambipolar charge transport can be generated by coassembling p-type semiconductors and n-type ones, and the charge-carrier mobility is now up to 1.57 cm 2 V −1 s −1 for holes and 0.47 cm 2 V −1 s −1 for electrons. [24] To date, these exciting results accelerate the investigations of organic functional cocrystals, such as room-temperature ferroelectricity, [25][26][27] optical waveguide properties, [28,29] pure organic room-temperature phosphorescent properties, [30][31][32] stimulusresponse (e.g., mechanical stress, [33,34] heat, [35,36] or solvent [37] ) characteristics, photovoltaics, [38] and near-infrared photothermal (PT) conversion and imaging, [39] etc.Cocrystal engineering with a noncovalent assembly feature by simple constituent units has inspired great interest and has emerged as an efficient and versatile route to construct functional materials, especially for the fabrication of novel and multifunctional materials, due to the collaborative strategy in the distinct constituent units. Meanwhile, the precise crystal a...

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Section: Rational Design and Controllable Preparation Of Organic Cocrmentioning

confidence: 89%

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

et al. 2019

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“…A quasi neutral (ρ ≈ 0.3) ms-CT crystal, DBTTF-TCNQ, does indeed exhibit appreciable hole and electron mobility [45,46], but other CT crystals do not. As a matter of fact, in ms-CT crystals electron correlations are important [42], and band theory might be inadequate to account for their behavior.…”

Section: Discussionmentioning

confidence: 99%

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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“…Yet, the formation of stacks and their packing is determined by more subtle, sometimes difficult to control, interactions. Letting aside the possibility of D:A ratios different from 1:1 [73], there are cases of a DA pair growing in either segregated or mixed stack, like tetramethyl-tetraselenofulvalene-TCNQ [79,80], or of the growth of different polymorphs with ms motif, as DBTTF-TCNQ [81,82]. Even the prototypical TTF-CA has at least two polymorphs, with quite different electronic properties [10,83].…”

Section: Discussionmentioning

confidence: 99%

Phenomenology of the Neutral-Ionic Valence Instability in Mixed Stack Charge-Transfer Crystals

2017

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Organic charge-transfer (CT) crystals constitute an important class of functional materials, characterized by the directional charge-transfer interaction between π-electron Donor (D) and Acceptor (A) molecules, with the formation of one-dimensional ...DADAD... stacks. Among the many different and often unique phenomena displayed by this class of crystals, Neutral-Ionic phase transition (NIT) occupies a special place, as it implies a collective electron transfer along the stack. The analysis of such a complex yet fascinating phenomenon has required many years of investigation, and still presents some open questions and challenges. We present an updated and extensive summary of the phenomenology of the temperature induced NIT, with emphasis on the spectroscopic signatures of the transition. A much shorter summary is given for the NIT induced by pressure. Finally, we report on the exploration, by chemical substitution, of the phase space of ...DADAD... CT crystals, aimed at finding materials with important semiconducting or ferroelectric properties, and at understanding the subtle factors determining the crystal packing.

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Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Cited by 85 publications

References 65 publications

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

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

Phenomenology of the Neutral-Ionic Valence Instability in Mixed Stack Charge-Transfer Crystals

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