Connecting molecule oxidation to single crystal structural and charge transport properties in rubrene derivatives

Uttiya, Sureeporn; Miozzo, Luciano; Fumagalli, E; Bergantin, Stefano; Ruffο, Riccardo; Parravicini, Matteo; Papagni, Antonio; Moret, Massimo; Sassella, A.

doi:10.1039/c3tc32527j

Cited by 26 publications

(41 citation statements)

References 59 publications

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“…1 calcd (P 2 1 /n) = 1.387 gcm À3 < 1 calcd (C 2/c) = 1.412 gcm À3 )( Figure 3). Thetetracenic core and the peripheric phenylene rings of staggered 2 are in close contact displaying distances of 349 and 356 pm, respectively.These findings for 2 are in line with structural motifs found for reported polymorphs of the parent tetracene molecule, [12,13] the tetracene derivative rubrene [13,17] or for higher homologue pentacene [16] as well as other related structures.…”

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confidence: 89%

Structural Polymorphism and Thin Film Transistor Behavior in the Fullerene Framework Molecule 5,6;11,12‐di‐o‐Phenylenetetracene

et al. 2016

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The molecular structure of the hydrocarbon 5,6;11,12-di-o-phenylenetetracene (DOPT), its material characterization and evaluation of electronic properties is reported for the first time.Asingle-crystal X-rays tudy reveals two different motifs of intramolecular overlap with herringbonetype arrangement displaying either face-to-edge or co-facial face-to-face packing depicting intensive p-p interactions. Density functional theory (DFT) calculations underpin that afavorable electronic transport mechanism occurs by acharge hopping process due to a p-bond overlap in the DOPT polymorph with co-facial arene orientation. The performance of polycrystalline DOPT films as active organic semiconducting layer in as tate-of-the-art organic field effect transistor (OFET) device was evaluated and proves to be film thickness dependent. For4 0nml ayer thickness it displays as aturation hole mobility (m hole )o fu pt o0 .01 cm 2 V À1 s À1 and an on/offratio (I on /I off )o f1.5 10 3 .The carbon framework in the title molecule is found as abasic structural motif in the fullerene molecules C 78 ,C 82 and C 84 (Figure 1). In addition, other symmetrical geodesic fullerene isomers bearing isolated pentagonal ring structures display molecular units of this conjugated polycycle. 5,6;11,12-di-o-phenylenetetracene (DOPT; 2)b elongs to the class of tetracene derivatives which have spurred interest over the last decade as model compounds with respect to an understanding of their chemistry as well as of their electronic properties like electronic structure and charge transport ability. [1,2] In the group of cyclo-pentafused polycyclica romatic hydrocarbons (PAH) 2 represents aprototypical acene framework molecule with peri-substitution closely related to tetracene,5,6,11,12-tetraphenyltetracenerubrene,orthe di-ophenylene substituted anthracene molecule rubicene. [2] Although, reported earlier in elusive experimental work [3] it was only very recently,that DOPT 2 was made accessible by Murata [4] and our group [5] in two independent and straightforward high yield synthetic approaches.Murata et al. presented ag eneral approach towards cyclo-pentafused polycyclic aromatics including DOPT-derivatives starting from the 5,11-diaryl-tetracene framework.[4] Shortly after,w ew ere able to devise agram-scale synthesis based on well established Diels-Alder chemistry for the parent molecule DOPT introducing as of ar unprecedented reductive double phenyl elimination.[5] Highly condensed PA Hm olecules like DOPT with their oftentimes energetically favorable molecular orbital ordering with small electronic band gap differences excel themselves as promising semiconducting organic materials for controlled charge transport. Thea fore mentioned close structural relationship of DOPT to the polyacene aromatic family especially the parent tetracene might promise interesting functional properties applicable in organic electronics like thin film transistors or future solar energy harvesting devices. [6] From asynthetic point of view the acene molecule DOPT i...

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confidence: 89%

Structural Polymorphism and Thin Film Transistor Behavior in the Fullerene Framework Molecule 5,6;11,12‐di‐o‐Phenylenetetracene

et al. 2016

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“…In practice, best‐performing semiconductors in OFETs tend to have IP s ranging from 5.1–5.3 eV because it is a good compromise between easy charge injection and stability versus oxidation . Compounds with IP < 5.1 eV tend to oxidize easily and their transport properties can be subject to oxygen doping . The difference between the ionization potential in solid state ( IP s ) minus the one obtained in gas phase ( IP g ) affords the polarization energy P + that evidently depends on the packing motif

P_{+} = I P_{s} - I P_{g}

…”

Section: Charge Transportmentioning

confidence: 99%

“…As a general matter of fact, external stimuli do not modify the very nature of charge transport mechanism, although in some cases, analytes act as impurities and react with charged species. In other cases, irradiation photodegrades organic semiconductors . A fast reaching conclusion of organic sensors and detectors is that each application requires a specific materials profile.…”

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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“…A substituted alkynyl aromatic ring (Scheme 2, red/boxed) guarantees a diagonal substitution on the B/C peripheral aryl rings, but altering 11's R-groups (Scheme 2, blue) such that they are not identical does not offer control of substitution placement on rubrene's tetracene backbone or its peripheral aryl rings. Sassella et al 22 similarly utilized the traditional method to form a series of A = D substituted rubrenes. By omitting the collidine addition and using tetrachloroethane as a solvent, rubrenes ( Table 2, entries 4-7) were produced in good yields (41-71%).…”

Section: Short Review Synthesismentioning

confidence: 99%

Synthesis and Crystal Engineering of Rubrene and Its Derivatives

2020

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Rubrene (5,6,11,12-tetraphenyltetracene) is a polyacene material that has been well studied throughout its nearly one-hundred year history. Originally found fascinating for its luminescent properties, it has emerged at the forefront for organic electronics due to its particularly high charge carrier mobility for an organic crystal. Despite great interest and its explosion in the literature over the past two decades, the commercial synthesis of rubrene has remained relatively unchanged since its initial discovery in 1926. Several recent studies have reported alternate routes to the rubrene structure with substitutions on the peripheral aromatic rings and tetracene core. Substituting in this manner has the potential to improve upon rubrene’s electronic properties. We review the various routes to rubrene and its derivatives and provide a brief overview of the solid-state library available for study. The information gained by comparing the solid-state properties between derivatives offers insight into unpredictable crystallization and polymorphism – complicated issues – which have hindered research into materials applications of rubrene. We hope that these insights inspire work in application-driven synthetic chemistry for future rubrene derivatives.1 Introduction2 Synthesis2.1 Traditional Rubrene Synthesis2.1.1 Recent Applications2.2 Multi-Step Synthesis2.2.1 Historical Routes2.2.2 Diels–Alder Approaches2.2.3 Cross-Coupling Approaches2.2.4 Comparative Synthesis of Perfluororubrene3 Crystal Engineering4 Conclusions and Outlook

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Connecting molecule oxidation to single crystal structural and charge transport properties in rubrene derivatives

Abstract: Stable rubrene derivatives displaying the same crystal packing features as orthorhombic rubrene are synthesized and their solid state properties studied.

Cited by 26 publications

References 59 publications

Structural Polymorphism and Thin Film Transistor Behavior in the Fullerene Framework Molecule 5,6;11,12‐di‐o‐Phenylenetetracene

Structural Polymorphism and Thin Film Transistor Behavior in the Fullerene Framework Molecule 5,6;11,12‐di‐o‐Phenylenetetracene

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

Synthesis and Crystal Engineering of Rubrene and Its Derivatives

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