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Kazuya Miyazaki, [Kyohei Matsuo](https://orcid.org/0000-0002-2472-9459), [Hironobu Hayashi](https://orcid.org/0000-0002-7872-3052), [Mitsuaki Yamauchi](https://orcid.org/0000-0003-0005-5960), [Naoki Aratani](https://orcid.org/0000-0002-3181-6526), [Hiroko Yamada](https://orcid.org/0000-0002-2138-5902)

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[An Unsymmetrical 5,15-Disubstituted Tetrabenzoporphyrin: Effect of Molecular Symmetry on the Packing Structure and Charge Transporting Property](https://mdr.nims.go.jp/datasets/730d75e7-6d37-42bd-ac29-fe922fcb6ef4)

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An Unsymmetrical 5,15-Disubstituted Tetrabenzoporphyrin: Effect of Molecular Symmetry on the Packing Structure and Charge Trans-porting Property Kazuya Miyazaki, Kyohei Matsuo,* Hironobu Hayashi, Mitsuaki Yamauchi, Naoki Aratani, Hiroko Yamada* Division of Materials Science, Graduate School of Science and Technology, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan Center for Basic Research on Materials, National Institute for Materials Science (NIMS), Sengen, Tsukuba, Ibaraki 305-0047, Japan Supporting Information Placeholder  ABSTRACT: Molecular design strategy to control the crystal structure of two-dimensionally (2D) p-extended organic semiconduc-tor has not been intensively explored. We synthesized an unsymmetric tetrabenzoporphyrin derivative (TIPS-Ph-BP) to demonstrate the effect of molecular symmetry on the crystal packing. TIPS-Ph-BP formed an antiparallel slipped p-stacking and 2D herringbone-like structure. Unsymmetric structure would make 2D p-stacking more stable than one-dimensional columnar structure to counteract steric and electronic imbalance in the crystal. As a result, TIPS-Ph-BP achieved the high hole mobility of 0.71 cm2 V–1 s–1. One of the key issues in the development of organic field-effect transistor (OFET) materials is the improvement of charge mobility. Since charge mobility depends on intermolecular in-teractions in solid state, it is important to control the crystal structure.1–4 In the current mainstream OFET materials such as acenes and heteroacenes, which have one-dimensionally (1D) extended polycyclic aromatic frameworks, the effect of substi-tution on the crystal structure has been intensively studied.5–9 For examples, alkyl chain substitutions typically provide layer-by-layer lamella structure, in which aromatic cores are arranged in a herringbone motif.10–13 On the other hand, some of bulky (trialkylsilyl)ethynyl substituted derivatives such as 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) have been known to afford the brickwork packing.14–17 In comparison, two-dimensionally (2D) extended p-conjugated molecules tend to form a sandwich herringbone, a cofacial herringbone, and a 1D columnar structure due to their enhanced p-p interaction.18,19 In addition, little is known about a versatile molecular design that would give a crystal structure suitable for OFET applica-tion.20–22 The 2D p-systems are expected to improve the thermal stability of the crystalline phase because molecular rotation in the crystal can be suppressed compared to linear acene ana-logues.23,24 Furthermore, it is possible to have optical absorption in the visible to near-infrared region, which has the potential to lead to the development of new functions, such as application to phototransistors.25 Tetrabenzoporphyrin (BP) is a useful building block as an organic semiconductor due to its chemical stability, large ab-sorption coefficient in visible region, and strong p-stacking in-teraction. We previously synthesized 5,15-bis(triisopropylsi-lylethynyl)tetrabenzoporphyrin (TIPS-BP), its metal complexes, and diazaporphyrin analogue (Figure 1a).26–29 Free-base TIPS-BP shows unique polymorphism with different p-stacking man-ners.30 One polymorph consists of 1D columnar p-stacking mo-tif and exhibited moderate maximum hole mobility of 0.027 cm2 V–1 s–1 for thin-film OFETs. In another polymorph, TIPS-BP forms the brickwork packing structure as TIPS-pentacene and exhibited excellent OFET properties with a maximum hole mobility of 1.1 cm2 V–1 s–1. However, most of its metal com-plexes and diazaporphyrin analogue formed 1D columnar  structure. In addition, even in the case of thin films with brick-work structure, it was necessary to carefully optimize the depo-sition conditions. Hence, a rational molecular design for selec-tive formation of 2D p-stacking of BP derivatives is desired. In this study, we devised a method to control the crystal structure of 5,15-substituted BP derivatives by structural modi-fication. 1D columnar packing and 2D brickwork packing of TIPS-BP consist of cross-stacking structure and slipped stack-ing structure, respectively (Figure S1). Because of the highly extended p-skeleton of BP, it is preferable to kinetically form cross-stack structure with large molecular overlap, thereby making the 1D columnar packing stable. If the substituents at 5- and 15-positions are different, i.e., unsymmetric derivatives, cross-stacking dimer is still kinetically favored, but the 1D co-lumnar structure grown from it would lose central and transla-tional symmetry. Thus, its aggregated crystal structure would be thermodynamically unfavorable because the steric and elec-trostatic imbalance could not be completely canceled (Figure 1b). On the other hand, if the molecules form slipped p-stacking in an antiparallel orientation, the steric and electrostatic imbal-ance could be counteract and the symmetry of the crystal struc-ture would be maintained even for the unsymmetric molecule. Therefore, we expected that a 2D packing structure suitable for OFETs would become thermodynamically stable for the un-symmetric derivatives. Recently, it was reported that unsym-metric substitution on the heteroacenes with an alkyl chain en-hances to form bilayer-type crystal structure.13,31,32 However, the effect of unsymmetric substitution on the crystal structure of 2D p-conjugated molecules has not been elucidated. Herein, we designed and synthesized an unsymmetric BP derivative TIPS-Ph-BP, which has two substituents of different sizes at meso positions (Figure 1a). Its bulky triisopropylsi-lylethynyl (TIPS-ethynyl) group can enhance solubility, while the other compact phenyl group, in an orthogonal configuration perpendicular to the BP skeleton, would inhibit the formation of face-to-face p-stacking and instead form slipped stacking. As expected, TIPS-Ph-BP showed 2D packing in its crystal struc-ture and the maximum hole mobility of the OFET prepared by drop-casting was 0.71 cm2 V–1 s–1, which is comparable to the hole mobility of TIPS-BP in 2D brickwork packing.   Figure 1. (a) Molecular structures of TIPS-BP and TIPS-Ph-BP. (b) Schematic representation of possible crystal structures for un-symmetric BP derivatives. Scheme 1 shows the synthesis of TIPS-Ph-BP. Unsymmet-ric TIPS-Ph-CP was synthesized as precursor by [2+2] acid-cat-alyzed condensation reaction using two kinds of aldehydes.33 Dipyrromethane 1 was treated with 3-(triisopropylsilyl)pro-piolaldehyde and benzaldehyde in the presence of borontrifluo-ride etherate, followed by oxidation with 2,3-dichloro-5,6-dicy-ano-1,4-benzoquinone (DDQ). Unsymmetric TIPS-Ph-CP was isolated by alumina column chromatography and recrystalliza-tion in 21% yield. This isolated yield is moderate compared to those of symmetric CP derivatives reported (7–57%24,26,33–35). Even so, this could be attributed to the intrinsic problem that the yield of unsymmetric products is statistically up to 50%. Then, TIPS-Ph-CP was heated at 200 °C in a glass tube oven under vacuum to afford TIPS-Ph-BP in 96%. The high thermal stabil-ity of TIPS-Ph-TBP was confirmed by thermogravimetry–dif-ferential thermal analysis (TG-DTA) (Figure S2). The 5% weight loss temperature (Td5) was 372 °C and no peaks were observed at temperatures below Td5 in the DTA curve. Scheme 1. Synthesis of TIPS-Ph-BP.  To reveal the electronic differences due to the substituent, the UV-visible absorption and fluorescence spectra of TIPS-Ph-BP in chloroform were measured and compared with those of TIPS-BP29 (Figure 2). As a result, both the Soret and Q bands in absorption spectrum of TIPS-Ph-BP blue-shifted. Similarly, the fluorescence wavelength blue-shifted from 716 nm to 690 nm. This would be due to the perpendicular configuration of the phenyl group with respect to BP skeleton, which results in con-tracted p conjugation than that of the ethynyl group. The abso-lute fluorescence quantum yield (FFL) and fluorescence lifetime (t) of TIPS-Ph-BP solution were 18% and 7.2 ns, respectively (Figure S3). According to these values, the radiative decay rate constant (kr) and nonradiative decay rate constant (knr) were cal-culated to be 2.5 × 107 s–1 and 1.1 × 108 s–1, respectively. The almost equivalent kr values for TIPS-Ph-BP and TIPS-BP (2.1 × 107 s–1) correspond with their comparable molar absorption coefficient (e) at first Q-band, while the smaller knr values for TIPS-Ph-BP than that of TIPS-BP (1.9 × 108 s–1) can be at-tributed to the suppression of intramolecular rotation by intro-duction of perpendicular Ph group. The cyclic voltammetry (CV) also revealed substitution effect on the electrochemical property. TIPS-Ph-BP exhibited two reversible oxidation waves of Eox = 0.10 and 0.31 V (vs. Fc/Fc+) and a reversible reduction wave of Ered = –1.61 V (Figure S4). Compared to the redox po-tential of TIPS-BP, the first Eox of TIPS-Ph-BP was positively shifted while its Ered was negatively shifted. This result suggests  that TIPS-Ph-BP has slightly larger HOMO–LUMO gap than TIPS-BP, similar to the blue-shift of its absorption wavelengths.  Figure 2. (a) UV-vis absorption and (b) fluorescence spectra of TIPS-Ph-BP and TIPS-BP in chloroform. (lex = 450 nm) The single crystals of TIPS-Ph-BP suitable for X-ray dif-fraction measurement were prepared from chloroform and oc-tane solution using a vapor diffusion method. The molecular structure and packing structure of TIPS-Ph-BP are shown in Figures 3 and S6-8. TIPS-Ph-BP had a bent TIPS-ethynyl group and a perpendicular Ph group. The dihedral angle between BP core and Ph group was 87.6°. Interestingly, BP core of TIPS-Ph-BP in the crystal was slightly contorted, unlike that of TIPS-BP which was highly planar. The dihedral angles between the two benzene rings across the free meso positions were 6.8° and 20.7°, respectively. In the crystal packing, TIPS-Ph-BP exhib-ited layered structure along the crystallographic a-axis (Figure S7). As expected, TIPS-Ph-BP formed a slipped p-stacking structure with an antiparallel manner in the layer (Figure 3a). Moreover, the BP cores are arranged in a herringbone-like motif (Figure 3b). A closer look at the p-stacking direction revealed two different stacking structures. In the pair A, the overlap of p-conjugated planes was large and the intermolecular distance between the BP centers was as close as 5.96 Å, whereas in the pair B, only one isoindole ring overlapped each other and the intermolecular distance was calculated to be 7.96 Å (Figure S8). Moreover, the interplane distance of 3.40 Å for pair A was slightly closer than that of 3.43 Å for pair B. These indicate that TIPS-Ph-BP has a local dimeric structure in the crystal like the sandwich herringbone structure. To discuss charge transport property in detail, the charge transfer integrals (t) of the HO-MOs between the neighboring molecular pairs were calculated using ADF program36 (Figure S9 and Table S4). Along the p-stacking direction (the crystallographic b-axis), the t values for pairs A and B were very different and were calculated to be 62.3 and 15.9 meV, respectively. On the other hand, t values along the crystallographic c-axis were moderate and in the range of 3.1–10.7 meV. Although the packing structure of TIPS-Ph-BP is not an ideal 2D electronic structure because of the nonequiv-alent t values in each direction, TIPS-Ph-BP is expected to show good hole mobility because the t values are above a certain level in any direction.   Figure 3. Crystal structures of TIPS-Ph-BP: (a) p-stacking struc-ture viewed along c-axis; (b) Packing structure viewed along a-axis. Substituents and hydrogen atoms are omitted for clarity.  We fabricated the OFET devices using TIPS-Ph-BP. After examining various deposition conditions, plate-like crystals were obtained reproducibly by slow vapor diffusion of octane into a chlorobenzene solution of TIPS-Ph-BP on the substrate. Then, source and drain electrodes (gold, 30 nm) were vacuum deposited on the obtained crystals to afford top-contact bottom-gate FETs (Figures S10 and S11). The transfer and output char-acteristics are shown in Figures 4 and S12. The OFETs showed the best and average hole mobilities of 0.71 and 0.55 cm2 V–1 s–1, respectively. This maximum mobility is slightly lower than 2.16 cm2 V–1 s–1 of single crystal FET of free-base TIPS-BP, but higher than 0.12 and 0.16 cm2 V–1 s–1 of its zinc(II) and cop-per(II) complexes, respectively.28 The out-of-plane X-ray dif-fraction measurement of the OFET device showed one diffrac-tion peak at 4.5°, which should correspond to the (100) diffrac-tion of single crystal structure (Figure S13). Furthermore, face index analysis of TIPS-Ph-BP based on the single crystal X-ray crystallography revealed that the crystal face with the largest area of the platelet crystal corresponds to the (100) face (Figure S5). These results suggest that the crystallographic bc plane, which contains p-stacking direction, is parallel to the substrate and current flow direction (Figure S14). Despite the herring-bone-like packing, hole mobility of TIPS-Ph-BP was moderate. This is probably due to the local dimeric structure in the crystal packing similar to the results for single crystal FETs of TIPS-BP metal complexes, where the long-range charge transport was suppressed by triad-like structure in columnar p-stacking.28   Figure 4. (a) Transfer and (b) output characteristics of the best-performing OFET using TIPS-Ph-BP. In summary, we have synthesized an unsymmetric 5,15-di-substituted BP derivative to study the influence of molecular symmetry on the crystal structure of 2D extended p-conjugated systems. TIPS-Ph-BP formed a dimeric herringbone packing consisting of slipped p-stacking with an antiparallel manner in the crystal. OFETs using TIPS-Ph-BP achieved the maximum hole mobility of 0.71 cm2 V–1 s–1 due to the partially 2D packing structure. This strategy could be used to control the crystal structures of various 2D extended p-conjugated systems. ASSOCIATED CONTENT  Data Availability Statement The data underlying this study are available in the published article and its Supporting Information. Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Experimental details, NMR and HRMS data, TG-DTA data, X-ray crystallographic data, photophysical and electrochemical data, and OFET characteristics (PDF)  Accession Codes CCDC 2286511 contains the supplementary crystallographic data for this paper. This data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing da-ta_re-quest@ccdc.cam.ac.uk, or by contacting The Cambridge Crystal-lographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. AUTHOR INFORMATION Corresponding Author Kyohei Matsuo – Institute for Chemical Research, Kyoto Univer-sity, Gokasho, Uji, Kyoto 611-0011, Japan; orcid.org/0000-0002-2472-9459; E-mail: matsuo.kyohei.2x@kyoto-u.ac.jp Hiroko Yamada – Institute for Chemical Research, Kyoto Univer-sity, Gokasho, Uji, Kyoto 611-0011, Japan; orcid.org/0000-0002-2138-5902; E-mail: hyamada@scl.kyoto-u.ac.jp Authors Kazuya Miyazaki – Division of Materials Science, Graduate School of Science and Technology, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan  Hironobu Hayashi – Center for Basic Research on Materials, Na-tional Institute for Materials Science (NIMS), Sengen, Tsukuba, Ibaraki 305-0047, Japan; orcid.org/0000-0002-7872-3052 Mitsuaki Yamauchi – Institute for Chemical Research, Kyoto Uni-versity, Gokasho, Uji, Kyoto 611-0011, Japan; orcid.org/0000-0003-0005-5960 Naoki Aratani – Division of Materials Science, Graduate School of Science and Technology, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan; or-cid.org/0000-0002-3181-6526 Notes The authors declare no competing financial interest. ACKNOWLEDGMENT  This work was partly supported by the JSPS KAKENHI Grant No. JP22K05255 for KM, JP22K19067 and JP23H01787 for NA, JP20H05833 and JP20H00379 for HY and by ISHIZUE 2023 of Kyoto University for HY. NMR measurements were supported by the Joint Usage/Research Center (JURC) at the Institute for Chem-ical Research, Kyoto University. We thank Ms. Akiko Fujihashi (Kyoto University) for HRMS measurements. REFERENCES (1) Coropceanu, V.; Cornil, J.; da Silva Filho, D. A.; Olivier, Y.; Silbey, R.; Brédas, J.-L. Charge Transport in Organic Semiconductors. Chem. Rev. 2007, 107, 926–952, (2) Mas-Torrent, M.; Rovira, C. Role of Molecular Order and Solid-State Structure in Organic Field-Effect Transistors. Chem. Rev. 2011, 111, 4833–4856, (3) Takimiya K.; Shinamura, S.; Osaka, I.; Miyazaki, E. Thieno-acene-Based Organic Semiconductors. Adv. Mater. 2011, 23, 4347–4370. (4) Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. 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