Characterization of New Rubrene Analogues with Heteroaryl

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Characterization of New Rubrene Analogues with Heteroaryl-Substituents Masashi Mamada, Hiroshi Katagiri, Tomo Sakanoue, and Shizuo Tokito Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg501519a • Publication Date (Web): 24 Nov 2014 Downloaded from http://pubs.acs.org on November 29, 2014

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Crystal Growth & Design

Characterization of New Rubrene Analogues with Heteroaryl-Substituents Masashi Mamada,*,† Hiroshi Katagiri,† Tomo Sakanoue,‡ Shizuo Tokito† †

Graduate School of Science and Engineering, Yamagata University, Yonezawa, Yamagata, 992-

8510 Japan ‡

Department of Applied Physics, Waseda University, Tokyo 169-8555 Japan

ABSTRACT New rubrene analogues, which are heteroaryl-tetrasubstituted tetracenes, have been developed using a simplified synthesis approach. Their stabilities in solution were improved compared to those of rubrene. The correlation among the molecular structures, crystal structures and charge transport properties has been investigated and compared with rubrene and various rubrene analogues. Although twisted structures of a tetracene backbone have often been found in single crystal analyses, the planarity might be related to intermolecular interactions rather than the electron donating/withdrawing properties of the heteroaryl side groups. The packing motifs in thiophene-substituted derivatives did not include -stacking of tetracene cores, which differ from the well-known structure of rubrene. However, furan-substituted derivatives can be crystallized in the -stacking manner. These differences in the packing structure affect hole transport properties.

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INTRODUCTION Rubrene (5,6,11,12-tetraphenyltetracene, Figure 1) is an attractive material for use as fluorescent dyes and solid hole conductor.1,2 Its hole mobility up to 40 cm2 V−1 s−1 has been the highest among organic semiconductors in recent years.3 Rubrene-based single crystal organic field-effect transistors (SC-OFETs) held a prominent role in the understanding of charge transport in molecular solids.4 However, the SC-OFETs are not well suited for practical applications in largearea flexible electronics due to its processing limitations. Recently, there are some examples of the OFET devices, which have comparable performance to single crystal devices, which can be processed through conventional solution processes using soluble organic semiconductors,5 however, solution-processed device based on a of rubrene layers exhibit very low field-effect mobilities.6,7 In addition to its poor electrical performance, rubrene has only modest solubility in organic solvents and rapidly decomposes in solution, making it largely incompatible with solution processing methods. While a number of organic semiconductors have so far been developed whereby small changes in their chemical structure can induce a large impact on their crystalline structure and electrical performance, the development of rubrene derivatives/analogues have been strictly limited in number.7,8 In fact, previous research reports reveal that the crystal structure of rubrene derivatives were highly dependent upon the side chains on aromatic rings. Therefore, there is a strong desire not only to develop new materials, but also to obtain further insights into the relationship among molecular structures, crystal structures, and physical properties. Although the heteroaryl rings such as thiophene rings are heavily used as building blocks to construct the organic semiconductors, we are aware of only one report in literature of the rubrene analogues with thiophene rings.9 Here, we report on four


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rubrene analogues with thiophene or furan rings (Figure 1), which were synthesized using newly established synthesis method for rubrene analogues. These compounds were characterized by single-crystal X-ray analysis and fabricating the field-effect transistor device to measure their electrical characteristics. R

R

X X

X X Rubrene

R

R

1 (TR0): X = S, R = H 2 (TR1): X = S, R = CH3 3 (FR0): X = O, R = H 4 (FR1): X = O, R = CH3

Figure 1. Chemical structures for rubrene and rubrene analogues 1–4.

EXPERIMENTAL SECTION General. Commercially available materials were used as received from the suppliers. Details of instruments, reagents, physical measurements, and computational calculations were shown in the Supporting Information section. Synthesis. Rubrene analogues 1–4 were synthesized from commercially available materials, and details are in the Supporting Information and in discussion of synthesis in the Results and Discussion section. X-ray Structure Analyses. Crystals suitable for X-ray crystallographic analysis were obtained from a solution of compounds 1–4 dissolved in dichloromethane in a round-bottom flask, which had been layered with methanol and allowed to stand overnight at room temperature. Suitable



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crystals were selected under Paratone® N (Hampton Research catalog number HR2-643), under ambient conditions and attached to the tip of a MiTeGen MicroMount©. X-ray diffraction data for compounds 1–4 were collected on a Rigaku Saturn 724 CCD diffractometer with Mo-K radiation ( = 0.71075 Å) at 93 K. Data collection, cell refinement, and data reduction were carried out using the CrystalClear-SM software. The structure was solved by direct methods using the program SHELXS-97, and refined by full-matrix least squares methods on F2 using SHELXL-97. All materials for publication were prepared by Yadokari-XG 2009 software. All non-hydrogen atoms were refined anisotropically. The positions of all hydrogen atoms were calculated geometrically and refined as a riding model. X-ray crystallographic information files (CIFs) are available for compound 1–4. CCDC nos. 1024133–1024138 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. OFET device fabrications. Bottom-contact/bottom-gate (BC/BG) and bottom-contact/top-gate (BC/TG) OFET devices for thin films of rubrene analogues 1–4 were fabricated and details are in the Supporting Information.

RESULTS AND DISCUSSION Rubrene possesses a relatively simple aromatic hydrocarbon structure with a C2h (2/m) symmetry. However, the synthesis of rubrene involves multistep reactions that includes nucleophilic addition, cycloaddition, phenyllithium additions and reductive aromatization.7,10,11 Moreover, the total yield of synthesis process is relatively low and harsh reagents such as boron tribromide are required during the procedure. Therefore, the development of a simplified and high-yielding


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synthesis route has been desired. Here, we have designed a novel one-pot synthesis based on Stille coupling reactions, as shown in Scheme 1. The C—C bond-forming cross-coupling reactions between the tetracene core and aryl groups are in fact the most straightforward strategy to form rubrene analogues with the same four side groups. Although most of Pd-mediated crosscoupling reactions such as Stille coupling and Suzuki-Miyaura coupling are only effective for aryl bromides and iodides, both retrosynthetic targets 5,6,11,12-tetrabromotetracene and 5,6,11,12-tetraiodotetracene are not available. However, a corresponding chloride 5,6,11,12tetrachlorotetracene was recently synthesized with good yield,12 and the recent progress with cross-coupling reactions has overcome the poor reactivity of the chlorides,13 making the adoption of tetrachlorotetracene for the Stille coupling reactions possible. In addition, cross-coupling reactions with tetrachlorotetracene using Grignard reagents can be found in a few reports.14 Here, the Stille coupling of tetrachlorotetracene and trialkylstannyl chalcogenophenes afforded the desired rubrene analogues in high yields without a formation of significant side products because chalcogenophenes are good nucleophiles. Products 1–4 were well soluble in common organic solvents, thus all of products were purified by column chromatography. Although the decomposition temperatures of compounds 1–4 are sufficiently high (336 °C for 1, 345 for 2, 316 for 3, and 313 for 4, Figure S1), these compounds slightly decomposed during sublimation even under vacuum conditions (10−3 Pa). Scheme 1. Synthesis of 1–4



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Single crystals of compounds 1–4 suitable for X-ray structural analysis were easily obtained by recrystallization from dichloromethane (DCM) layered with methanol or sublimation. Compounds 1 and 2 resulted in bright red crystals, which form plate-like shapes in 1 and blocklike shapes in 2. However, compound 4 exhibited dark red, needle-shaped crystals. The crystals for compound 3 (Figure 1) are similar to compound 1 (plate-like) and compound 4 (needle-like), suggesting the presence of polymorphs. In fact, crystal packing motifs are broadly divided, depending on whether the tetracene core has - stacking interactions or not (Figure 2). The crystal structures for compounds 1, 2 and 3 (crystal form I, plate-like, triclinic polymorph) showed CH- intermolecular interactions without a -stacking arrangement between tetracene cores. Conversely, - stacking structures were observed along the a-axis for 3 (crystal form II, needle-like, monoclinic polymorph) and c-axis for 4, which is somewhat similar to the packing motif for rubrene and is preferable for charge transport. The key crystallographic parameters for compounds 1–4 are provided in Table 1. Note that the crystal structure for compound 1 has been reported previously in literature, whereby the structure was resolved in the monoclinic space group P21 with crystal disorder in the thiophene rings.9 The crystal structures for compound 1 from both recrystallization and sublimation that are presented here were found in the space group P21/c without disorder of the thiophene rings, having nearly the same intermolecular interactions as the reported structure. Interestingly, compound 3 crystallizes in one of two polymorphs depending on the polarity of the solvents used for the recrystallization. When the solvent is less polar (dielectric constant 3.5 Å. The close proximity is attributed to an avoidance of steric repulsions of side aryl groups by the twisted structures. In addition, the calculated packing index of 70.4% for 3 and 69.6% for 4, which were made using PLATON/VOID software, are comparable to 71.0% for rubrene crystal.17 Although the rubrene derivatives with the twisting tetracene cores have not yet applied to the organic electronic devices, compounds 3 and 4 are considered to be promising materials for this application.



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microscope iimages of crystalline sttructures forr (a) 1, (b) 22, (c) 3, and (d) 4 Figure 1. Optical m f dichlorromethane/m methanol. grown from

Figure 2. Packing arrangemen a nts of (a) 1, ((b) 2, (c) 3 ((crystal form m I), (d) 3 (ccrystal form m II) along with thee a-axis, (e) 4 along witth the c-axiss, (f) 3 (crysstal form II) as seen dow wn the shortt molecullar axis, andd (g) 4 as seeen down thee short moleecular axis ((thermal elliipsoids 50% % probabillity). Disordder molecules in 2 and 3 (crystal foorm I) are om mitted for cclarity.


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Table 1. Crystal Data for Compounds 1–4 Parameters

1

2

3 Form I

3 Form II

4

crystal description

platelet

block

platelet

needle

needle

crystal system

monoclinic

orthorhombic triclinic

P21/c

space group

P212121

monoclinic

P1̅

triclinic

P21/c

P1̅

a (Å)

13.601 (2)

9.599 (7)

10.553 (3)

14.386 (4)

8.5037 (18)

b (Å)

9.2479 (15)

13.287 (10)

11.340 (3)

8.452 (2)

13.244 (2)

c (Å)

20.718 (3)

25.015 (19)

16.568 (6)

21.794 (5)

14.277 (3)

 (°)

90.00

90.00

83.481 (13)

90.00

62.458 (8)

 (°)

92.771 (2)

90.00

89.450 (15)

116.994 (14) 80.781 (11)

 (°)

90.00

90.00

64.275 (1)

90.00

74.581 (10)

density (g cm−3)

1.421

1.276

1.384

1.385

1.327

4

4

3

4

2

Z R1 [I > 2(I)] (%)

0.0501

0.0777

0.0459

0.0460

0.0450

CCDC No.

1024133

1024135

1024136

1024137

1024138



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mined by the C—C bonnd at end Figure 33. The torsion angles allong the tetrracene backkbone determ positionns for (a) 1, (b) 2, (c) 3 (crystal form m I), (d) 3 (crystal form m II) and (e) 4. Acenes and their dderivatives, including ruubrene, fundamentally suffer from m instability due to miconductors is criticall to enablingg solution photooxxidation in aair.18 Photocchemical staability of sem processees for printeed device appplications bbecause imppurities will seriously ddegrade the eelectronic transporrt propertiess.19 Thereforre, the stabiility of comppounds 1–4 were evaluuated using tthe UVVis specctra under w white room llight in an aair ambient. Figure 4 annd Figure S22 clearly shoows higher pphotooxidatiion stabilityy for compouunds 1–4 inn comparisonn to rubrenee. The absorrption bands att around 5000 nm for thee rubrene soolution disapppeared afteer a few houurs. Howeveer, there were noo significantt changes in the absorpttion bands fo for compounnds 1–3, andd their specttra were overlappped even aft fter 24 hourss. Although small changges were obbserved in coompound 4,, they occurredd much morre slowly thhan rubrene and were suufficiently sttable for preeparation off a semiconnducting inkk. This anti-photooxidattion feature would be aadvantageouus for use inn organic electronnic devices.


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o time for (a) 1, (b) 22, (c) 3, (d) 4 and (e) Figure 4. UV-Vis absorption spectra as a function of rubrene in dichloromethane. The eleectrochemical behavior of compounnds 1–4 wass investigateed by cyclicc voltammettry (CV, Table 2 and Figure S3). It is innteresting to note that coompounds 1–4 1 show ann irreversiblle oxidatioon peak, which differs ffrom the quaasi-reversible oxidationn wave of teetracene andd the reversibble oxidationn wave of ruubrene,20 inddicating thaat substitutioons of thiophhene and fuuran do not helpp stabilize thhe radical caation on the tetracene coore under thhe voltammeetric conditiions. The highest occupied m molecular orbbital (HOM MO) energy levels l for coompounds 1––4 as estimaated from the oxiddation onsets are: −5.244 eV, −5.09 eV, −5.19 eV, e and −4.998 eV, respeectively. Byy compariing the HOM MO levels aand the loweest unoccupied molecullar orbital (L LUMO) levvels of



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rubrene (−5.13 eV and −2.73 eV), compounds 1 and 3 have slightly lower lying HOMO levels. However, the additional substitutions of electron-donating methyl group for compounds 2 and 4 shift the HOMO levels to higher levels. At any rate, the HOMO energy levels of all compounds lie close to the work function of gold (−5.1 eV), therefore these compounds are expected to have good hole injection properties from gold electrodes, while behaving as a p-type organic semiconductor. The calculated HOMO-LUMO levels (B3LYP/6-31G(d,p) level) are shown in Table 2 and Figure S4, where the tetracene rings were optimized is a nonplanar conformation.21 Although the HOMO level of rubrene is largely delocalized on the tetracene core, the HOMO levels for compounds 1–4 spread partly due to the thiophene and furan rings. Thus, interactions through the thiophene and furan rings may contribute to the charge transport with increasing dimensionality. Table 2. Photophysical and Electrochemical Properties for Compounds 1–4.

(nm)a

abs

Eox (V)b,c

Ered (V)b,d

HOMO (eV)e

LUMO (eV)e

solution

505, 539

0.44

−1.83

−5.24

−2.97

calcdf

590

−

−

−4.80

−2.44

solution

509, 543

0.29

−1.87

−5.09

−2.93

calcdf

596

−

−

−4.66

−2.27

solution

511

0.39

−1.75

−5.19

−3.05

calcdf

590

−

−

−4.68

−2.29

solution

535

0.18

−1.82

−4.98

−2.98

calcdf

606

–

–

4.50



compd 1

2

3

4

a

The lowest energy maxima. b Determined by cyclic voltammetry measurement in a 0.1 M solution of Bu4NClO4 in dichloromethane at rt (vs Fc/Fc+). c Onset potential. d Half-wave potential. e Estimated vs vacuum level from EHOMO = 4.80 – Eox or ELUMO = 4.80  Ered. f Calculated by DFT methods at the B3LYP/6-31G(d,p) level using Gaussian 09 program.


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The OFET devices were fabricated with bottom-contact/bottom-gate (BC/BG) and bottomcontact/top-gate (BC/TG) configurations (Figure S5). Thin films of rubrene and rubrene analogues 1–4 were deposited by drop-casting solution ranging from 0.1–0.2 wt% in the indicated solvents onto the FET device channel region, where pentafluorobenzenethiol (PFBT)treated gold source-drain electrodes on a cross-linked poly-4-vinylphenol (PVP) dielectric are enclosed by Teflon bank structure. The initial evaluation of compounds 1–4 using a BC/BG device showed a clear difference, whereby the thin film layers of 4 from chloroform solution showed semiconducting behavior, whereas thin films of 1–3 and rubrene exhibited no gate bias effect. As expected, rubrene layers prepared by solution methods were difficult to use a semiconductor due to an amorphous film-forming ability (Figure S8) and differing solid-state structures than vacuum-deposited layers.22 The hole mobility for compound 3 was 1.4 × 10−3 cm2 V−1 s−1 with a threshold voltage of −3 V and on/off current ratio of 8 × 104. Although this level of device performance only moderately good, it was found that twisted tetracene cores can provide charge transport paths and -stacking interactions, which is an important factor as a matter of course. The OFET devices were investigated further using the BC/TG device configuration. The TG devices are capable to adopt fluoropolymers such as CYTOP™ for the dielectric layer, which have the low dielectric constant and the low interface trap sites.23 Therefore, the TG structure generally provides for better electrical performance. In fact, the OFET device using compound 4 in a BC/TG configuration showed a slightly better mobility of 3.8 × 10−3 cm2 V−1 s−1 for a layer formed from a chloroform solution. In addition, other compounds also worked as p-type semiconductors in BC/TG devices, with the exception of rubrene. The device performance levels for compounds 1–4 are summarized in Table 3. The



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device performance for compound 4 is better than those of other compounds, presumably because of the differences in intermolecular arrangements and packing structures, and the formation of single crystalline domains in the entire channel region even from the solution processes (Figure 5 and Figure S8). Note that crystalline growth in the small area of the channel region is very complicated because there are several surrounding interfaces, including the PVP dielectric, PFBT-treated gold electrode and Teflon bank layer. Therefore, molecular arrangement over the entire domain of the thin film layer cannot be conclusively identified as those in a single crystal. The implication of such correlation between the device performance and the intermolecular interactions requires more careful discussion, especially for compounds with the polymorphs, such as compound 3 and rubrene. The device of using layer from compound 3 in polar acetone solution gave slightly better mobility compared to that in chloroform, although the mobility in a polar dimethylformamide (DMF) solution remained nearly the same. These results indicate that thin film layer from compound 3 may be difficult to classify into two polymorph structures, as observed in the single crystal analysis. Meanwhile, compound 4 showed improved performance in a DMF solution and a maximum mobility of approximately 0.01 cm2 V−1 s−1 was obtained (Figure 6).


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FET Characcteristics forr Compoundds 1–4. Table 33. BC/TG OF compdd

Solvennta

µ (cm m2 V−1 s−1)

on/off ratioo

Vth (V V)

1

CHCll3

2.3 × 10−4

1 × 103

−8

2

CHCll3

9.0 × 10−5

4 × 102

−9

3

CHCll3

5.9 × 10−4

2 × 104

−23

Acetonne

1.5 × 10−3

2 × 103

−7

Toluenne

8.6 × 10−5

2 × 102

−51

DMF F

5.0 × 10−4

2 × 103

−23

CHCll3

3.8 × 10−3

1 × 104

−13

Acetonne

2.9 × 10−3

8 × 103

−9

Toluenne

3.3 × 10−3

1 × 104

−20

DMF F

8.7 × 10−3

4 × 104

−12

4

rubrenee

CHCll3

no gate effect

a

Thinn films werre depositedd by drop-caasting from m the 0.1–0.2 wt% soluution in the indicated solventss

Figure 5. (a) The bbright-field m microscope image and (b) the cross-polarlizedd microscoppe image for thin film layer of o compound 4 drop-casted from a DMF soluttion.



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(a)

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(b)

Figure 6. (a) Transfer and (b) output characteristics of BC/TG device for thin film layer of compound 4 drop-casted from a DMF solution (thickness of CYTOP dielectric layer is ~600 nm).

CONCLUSIONS We have successfully synthesized a series of heteroaryl-substituted rubrene analogues through Stille coupling reactions. The characteristic features of developed rubrene analogues are: (1) good solubility for the preparation semiconducting inks; (2) better stability in solution compared to rubrene; (3) suitable HOMO energy levels for the injection of hole carriers from gold electrodes; (4) a -stacking arrangement for furan-substituted derivatives with a twisted core; (5) moderately good hole mobility on the order of 10−3 cm2 V−1 s−1 was observed for solutionprocessed OFET devices, whereas rubrene showed no gate bias effect under the same conditions. The electrical performance attained for the devices would seem to imply a correlation between the packing structures and carrier transporting properties. These results indicate that rubrene


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analogues with further modifications could be good choices as solution-processable semiconductors in printed electronics applications.

ASSOCIATED CONTENT Supporting Information. Full experimental details, synthesis, characterization data, computational data, device characterizations and crystallographic details are available in the Supporting Information. This information is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (M.M.) ACKNOWLEDGMENT We thank Prof. C. Shepherd for helpful discussions. This work was financially supported by the Grant-in-Aid for Young Scientists (B) (26810106) from the Japan Society for the Promotion of Science (JSPS), the Grant-in-Aid for challenging Exploratory Research (26600048) from JSPS, the Japan Regional Innovation Strategy Program by the Excellence (creating international research hub for advanced organic electronics) of Japan Science and Technology Agency (JST), and by the Ministry of Education, Culture, Sports, Science and Technology, Japan.



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For Taable of C Contents O Only Characcterizationn of New Rubrene R A Analogues w with Heteroaryl-Subbstituents Masashii Mamada,** Hiroshi Kaatagiri, Tom mo Sakanouee, Shizuo Tookito

w rubrene aanalogues arre introduceed. The crystal structurees for furan--substituted Four new tetracennes display a - stackinng arrangem ment, althouugh the tetracene core has a twistedd conform mation. Soluution-processed organicc field-effectt transistors (OFETs) shhowed carriier mobilitiies of up to aapproximately 0.01 cm m2 V−1 s−1. W We concludee that solid-sstate crystall packing appears to be correllated with ccarrier mobillity in organnic field-efffect transistoors.

PSIS SYNOP


Characterization of New Rubrene Analogues with Heteroaryl

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