The crystal structures of organic semiconductors are critical when they are integrated into optoelectronic devices, such as organic field-effect transistors (OFETs). In this study, we introduce a crystal engineering approach that leverages weak, nondirectional dispersion forces and steric effects, working together to govern the molecular packing. We investigated how the substitution at the peri-position affects the crystal structure in a series of oligorylene molecules. Upon elucidation of the crystal structures, we found a distinct difference between symmetrical and unsymmetrical derivatives. The unsymmetrical derivatives are prone to forming a sandwich herringbone (SHB) motif, while symmetrical derivatives exhibit a typical herringbone (HB) motif. In most of the rylene derivatives, substitutions at the peri-position triggered an "end-to-face" orientation within the HB structure, rather than an "edge-to-face" orientation, which occurs more often. Results from the Hirschfeld surface analysis provide evidence that the "end-to-face" orientation promotes C-H-π interactions between terminal methyl groups and the π-core of the molecules. While these C-Hmethyl---π interactions contribute to the overall stability of the packing structure, they remain ineffective in enhancing the charge transport properties. In contrast, a particular derivative, tetramethyl perylene (TMP), exhibits a HB structure with an edge-to-face orientation, promoting both C-H---π and π---π interactions. These interactions are crucial for improving the charge carrier mobility, as evidenced by mobility values. For TMP, we could obtain the mobility value of 0.05 cm2 V-1 s-1 in OFETs, whereas a slightly higher mobility of 0.2 cm2 V-1 s-1 was observed with Field-Induced Time-Resolved Microwave conductivity (FI-TRMC) technique.

BASF SE RGD J542S am Rhein Ludwigshafen 67056 Germany

Department of Chemistry University of Rochester Rochester New York 14627 United States

Department of Molecular Engineering Graduate School of Engineering Kyoto University Kyoto 615 8510 Japan

Department of Structure Analysis Institute of Physics Czech Academy of Sciences Na Slovance 2 1999 Prague 8 18221 Czech Republic

Dipartimento di Chimica G Ciamician Via Selmi 2 Università di Bologna Bologna 1 40126 Italy

Dynamic Molecular Materials Laboratory Dipartimento di Scienze della Vita Università degli Studi di Modena e Reggio Emilia Via Campi 103 Modena 41125 Italy

erConTec GmbH Roter Turm Weg 3 Wachenheim an der Weinstrasse 67157 Germany

Institut für Physik and IRIS Adlershof Humboldt Universitat zu Berlin Berlin 12489 Germany

International Solvay Institutes ULB CP 231 Boulevard du Triomphe Bruxelles 1050 Belgium

Laboratory for Chemistry of Novel Materials University of Mons Mons 7000 Belgium

Laboratory of Polymer Chemistry Université Libre de Bruxelles Boulevard du Triomphe Bruxelles 1050 Belgium

University of Strasbourg CNRS ISIS UMR 7006 8 Alleé Gaspard Monge Strasbourg 67000 France

WEL Research Institute avenue Pasteur 6 Wavre 1300 Belgium

See more in PubMed

Desiraju G. R.; Gavezzotti A. Crystal Structures of Polynuclear Aromatic Hydrocarbons. Classification, Rationalization and Prediction from Molecular Structure. Acta Crystallographica Section B 1989, 45 (5), 473–482. 10.1107/S0108768189003794. DOI

Desiraju G. R. Crystal Engineering: Solid State Supramolecular Synthesis. Curr. Opin. Solid State Mater. Sci. 1997, 2 (4), 451–454. 10.1016/S1359-0286(97)80088-5. DOI

Desiraju G. R. Designer Crystals: Intermolecular Interactions, Network Structures and Supramolecular Synthons. Chem. Commun. 1997, (16), 1475–1482. 10.1039/a607149j. DOI

Bishop R. Organic Crystal Engineering beyond the Pauling Hydrogen Bond. CrystEngComm 2015, 17 (39), 7448–7460. 10.1039/C5CE01069A. DOI

Solà M. Forty Years of Clar’s Aromatic π-Sextet Rule. Front Chem. 2013, 1, 66422.10.3389/fchem.2013.00022. PubMed DOI PMC

Razus A. C. Azulene Moiety as Electron Reservoir in Positively Charged Systems; a Short Survey. Symmetry 2021, 13 (4), 526.10.3390/sym13040526. DOI

Markiewicz J. T.; Wudl F. Perylene, Oligorylenes, and Aza-Analogs. ACS Appl. Mater. Interfaces 2015, 7 (51), 28063–28085. 10.1021/acsami.5b02243. PubMed DOI

Würthner F.; Saha-Möller C. R.; Fimmel B.; Ogi S.; Leowanawat P.; Schmidt D. Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials. Chem. Rev. 2016, 116 (3), 962–1052. 10.1021/acs.chemrev.5b00188. PubMed DOI

Müllen K. Evolution of Graphene Molecules: Structural and Functional Complexity as Driving Forces behind Nanoscience. ACS Nano 2014, 8 (7), 6531–6541. 10.1021/nn503283d. PubMed DOI

Simmons G. L.; Lingafelter E. C. The Crystal Structure of Pyracene. Acta Crystallogr. 1961, 14 (8), 872–874. 10.1107/S0365110X61002515. DOI

Ehrlich H. W. W. A Refinement of the Crystal and Molecular Structure of Acenaphthene. Acta Crystallogr. 1957, 10, 699–705. 10.1107/S0365110X5700242X. DOI

Koch K.-H.; Müllen K. Polyarylenes and Poly(Arylenevinylene)s, V. Synthesis of Tetraalkyl-Substituted Oligo(1,4-Naphthylene)s and Cyclization to Soluble Oligo(Peri-Naphthylene)S2). Chem. Ber. 1991, 124 (9), 2091–2100. 10.1002/cber.19911240935. DOI

Pigulski B.; Ximenis M.; Shoyama K.; Würthner F. Synthesis of Polycyclic Aromatic Hydrocarbons by Palladium-Catalysed [3 + 3] Annulation. Org. Chem. Front. 2020, 7 (19), 2925–2930. 10.1039/D0QO00968G. DOI

Tanaka J. The Electronic Spectra of Aromatic Molecular Crystals. II. The Crystal Structure and Spectra of Perylene. Bull. Chem. Soc. Jpn. 1963, 36 (10), 1237–1249. 10.1246/bcsj.36.1237. DOI

Li T.; Zhang C. Z.; Su Y. X.; Niu M. X.; Gu C. Y.; Song M. X. Crystal Structure and Optoelectronic Properties of Antiaromatic Compound 3,4,9,10-Tetrahydrodicyclopenta[Cd,Lm]Perylene. Crystallography Reports 2017, 62 (6), 885–888. 10.1134/S1063774517060165. DOI

Anderson A. G.; Wade R. H. The Synthesis of Pyracene. J. Am. Chem. Soc. 1952, 74 (9), 2274–2278. 10.1021/ja01129a032. DOI

EatonMillerMarguliesShoerSchaller S. W. S. A. E. A. L. E. R. D.; Wasielewski M. R. S. A.; Margulies E.; Shoer E.; Schaller L. D. R.; Wasielewski R.; Singlet M. Singlet Exciton Fission in Thin Films of tert-Butyl-Substituted Terrylenes. J. Phys. Chem. A 2015, 119 (18), 4151–4161. 10.1021/acs.jpca.5b02719. PubMed DOI

Pookpanratana S. J.; Goetz K. P.; Bittle E. G.; Haneef H.; You L.; Hacker C. A.; Robey S. W.; Jurchescu O. D.; Ovsyannikov R.; Giangrisostomi E. Electronic Properties and Structure of Single Crystal Perylene. Org. Electron. 2018, 61, 157–163. 10.1016/j.orgel.2018.05.035. PubMed DOI PMC

Pick A.; Klues M.; Rinn A.; Harms K.; Chatterjee S.; Witte G. Polymorph-Selective Preparation and Structural Characterization of Perylene Single Crystals. Cryst. Growth Des. 2015, 15 (11), 5495–5504. 10.1021/acs.cgd.5b01130. DOI

Datta A.; Mohakud S.; Pati S. K. Comparing the Electron and Hole Mobilities in the α and β Phases of Perylene: Role of π-Stacking. J. Mater. Chem. 2007, 17 (19), 1933–1938. 10.1039/B700625J. DOI

Sato K.; Katoh R. Fluorescence Properties of β-Perylene Crystals Prepared by a Physical Vapor Transport Method under Atmospheric Pressure. Chem. Phys. Lett. 2019, 730, 312–315. 10.1016/j.cplett.2019.06.031. DOI

Friedlein R.; Crispin X.; Pickholz M.; Keil M.; Stafström S.; Salaneck W. R. High Intercalation Levels in Lithium Perylene Stoichiometric Compounds. Chem. Phys. Lett. 2002, 354 (5), 389–394. 10.1016/S0009-2614(02)00148-3. DOI

Wang C.; Abbas M.; Wantz G.; Kawabata K.; Takimiya K. Heavy-Atom Effects” in the Parent [1] Benzochalcogenopheno [3, 2-b][1] Benzochalcogenophene System. J. Mater. Chem. C Mater. 2020, 8 (43), 15119–15127. 10.1039/D0TC01408G. DOI

Hsieh C. T.; Chen C. Y.; Lin H. Y.; Yang C. J.; Chen T. J.; Wu K. Y.; Wang C. L. Polymorphic Behavior of Perylene and Its Influences on OFET Performances. J. Phys. Chem. C 2018, 122 (28), 16242–16248. 10.1021/acs.jpcc.8b02199. DOI

Pensack R. D.; Purdum G. E.; Mazza S. M.; Grieco C.; Asbury J. B.; Anthony J. E.; Loo Y.-L.; Scholes G. D. Excited-State Dynamics of 5,14- vs 6,13-Bis(Trialkylsilylethynyl)-Substituted Pentacenes: Implications for Singlet Fission. J. Phys. Chem. C 2022, 126 (23), 9784–9793. 10.1021/acs.jpcc.2c00897. PubMed DOI PMC

Wang X.; Liu X.; Cook C.; Schatschneider B.; Marom N. On the Possibility of Singlet Fission in Crystalline Quaterrylene. J. Chem. Phys. 2018, 148 (18), 184101.10.1063/1.5027553. PubMed DOI

Gsänger M.; Bialas D.; Huang L.; Stolte M.; Würthner F. Organic Semiconductors Based on Dyes and Color Pigments. Adv. Mater. 2016, 28 (19), 3615–3645. 10.1002/adma.201505440. PubMed DOI

Würthner F.; Stolte M. Naphthalene and Perylene Diimides for Organic Transistors. Chem. Commun. 2011, 47 (18), 5109–5115. 10.1039/c1cc10321k. PubMed DOI

Chen Z.; Debije M. G.; Debaerdemaeker T.; Osswald P.; Würthner F. Tetrachloro-Substituted Perylene Bisimide Dyes as Promising n-Type Organic Semiconductors: Studies on Structural, Electrochemical and Charge Transport Properties. ChemPhysChem 2004, 5 (1), 137–140. 10.1002/cphc.200300882. PubMed DOI

Palatinus L.; Brázda P.; Jelínek M.; Hrdá J.; Steciuk G.; Klementová M. Specifics of the Data Processing of Precession Electron Diffraction Tomography Data and Their Implementation in the Program PETS2.0. Acta Crystallographica Section B 2019, 75 (4), 512–522. 10.1107/S2052520619007534. PubMed DOI

Brázda P.; Klementová M.; Krysiak Y.; Palatinus L. Accurate Lattice Parameters from 3D Electron Diffraction Data. I. Optical Distortions. IUCrJ. 2022, 9 (6), 735–755. 10.1107/S2052252522007904. PubMed DOI PMC

Klar P. B.; Krysiak Y.; Xu H.; Steciuk G.; Cho J.; Zou X.; Palatinus L. Accurate Structure Models and Absolute Configuration Determination Using Dynamical Effects in Continuous-Rotation 3D Electron Diffraction Data. Nat. Chem. 2023, 15 (6), 848–855. 10.1038/s41557-023-01186-1. PubMed DOI PMC

Palatinus L.; Petříček V.; Corrêa C. A. Structure Refinement Using Precession Electron Diffraction Tomography and Dynamical Diffraction: Theory and Implementation. Acta Crystallogr., Sect. A 2015, 71 (2), 235–244. 10.1107/S2053273315001266. PubMed DOI

Petříček V.; Palatinus L.; Plášil J.; Dušek M.. Jana2020 – a New Version of the Crystallographic Computing System Jana. 2023, 238 ( (7–8), ), 271–282. DOI: 10.1515/zkri-2023-0005. DOI

Macrae C. F.; Sovago I.; Cottrell S. J.; Galek P. T. A.; McCabe P.; Pidcock E.; Platings M.; Shields G. P.; Stevens J. S.; Towler M.; Wood P. A. Mercury 4.0: From Visualization to Analysis, Design and Prediction. J. Appl. Crystallogr. 2020, 53 (1), 226–235. 10.1107/S1600576719014092. PubMed DOI PMC

Giannini S.; Blumberger J. Charge Transport in Organic Semiconductors: The Perspective from Nonadiabatic Molecular Dynamics. Acc. Chem. Res. 2022, 55 (6), 819–830. 10.1021/acs.accounts.1c00675. PubMed DOI PMC

Abd El-Aal H. A. K.; Khalaf A. A. Modern Friedel-Crafts Chemistry. Part 38. Facile Synthesis of Acenaphthenes via Direct and Rearranged Intramolecular Friedel-Crafts Cyclialkylations of Intermediate Carbinols. Polycycl Aromat Compd 2013, 33 (4), 331–346. 10.1080/10406638.2013.781041. DOI

Rickhaus M.; Belanger A. P.; Wegner H. A.; Scott L. T. An Oxidation Induced by Potassium Metal. Studies on the Anionic Cyclodehydrogenation of 1,1′-Binaphthyl to Perylene. J. Org. Chem. 2010, 75 (21), 7358–7364. 10.1021/jo101635z. PubMed DOI

Jackson K. A.; Hunt J. D. Transparent Compounds That Freeze like Metals. Acta Metall. 1965, 13 (11), 1212–1215. 10.1016/0001-6160(65)90061-1. DOI

Warta W.; Karl N. Hot Holes in Naphthalene: High, Electric-Field-Dependent Mobilities. Phys. Rev. B 1985, 32 (2), 1172–1182. 10.1103/PhysRevB.32.1172. PubMed DOI

McKinnon J. J.; Spackman M. A.; Mitchell A. S. Novel Tools for Visualizing and Exploring Intermolecular Interactions in Molecular Crystals. Acta Crystallogr. B 2004, 60 (6), 627–668. 10.1107/S0108768104020300. PubMed DOI

Hall C. L.; Andrusenko I.; Potticary J.; Gao S.; Liu X.; Schmidt W.; Marom N.; Mugnaioli E.; Gemmi M.; Hall S. R. 3D Electron Diffraction Structure Determination of Terrylene, a Promising Candidate for Intermolecular Singlet Fission. ChemPhysChem 2021, 22 (15), 1631–1637. 10.1002/cphc.202100320. PubMed DOI PMC

Koch N.; Salzmann I.; Johnson R. L.; Pflaum J.; Friedlein R.; Rabe J. P. Molecular Orientation Dependent Energy Levels at Interfaces with Pentacene and Pentacenequinone. Org. Electron. 2006, 7 (6), 537–545. 10.1016/j.orgel.2006.07.010. DOI

Duhm S.; Heimel G.; Salzmann I.; Glowatzki H.; Johnson R. L.; Vollmer A.; Rabe J. P.; Koch N. Orientation-Dependent Ionization Energies and Interface Dipoles in Ordered Molecular Assemblies. Nat. Mater. 2008, 7 (4), 326–332. 10.1038/nmat2119. PubMed DOI

Schweicher G.; Garbay G.; Jouclas R.; Vibert F.; Devaux F.; Geerts Y. H.. Molecular Semiconductors for Logic Operations: Dead-End or Bright Future?. Adv. Mater. 2020, 32( (10), )10.1002/adma.201905909. PubMed DOI

Margulies E. A.; Miller C. E.; Wu Y.; Ma L.; Schatz G. C.; Young R. M.; Wasielewski M. R. Enabling Singlet Fission by Controlling Intramolecular Charge Transfer in π-Stacked Covalent Terrylenediimide Dimers. Nat. Chem. 2016, 8 (12), 1120–1125. 10.1038/nchem.2589. PubMed DOI

Takimiya K.; Osaka I.; Mori T.; Nakano M. Organic Semiconductors Based on [1]Benzothieno[3,2-b][1]Benzothiophene Substructure. Acc. Chem. Res. 2014, 47 (5), 1493–1502. 10.1021/ar400282g. PubMed DOI

Fratini S.; Mayou D.; Ciuchi S. The Transient Localization Scenario for Charge Transport in Crystalline Organic Materials. Adv. Funct. Mater. 2016, 26 (14), 2292–2315. 10.1002/adfm.201502386. DOI

Fratini S.; Ciuchi S.; Mayou D.; De Laissardière G. T.; Troisi A. A Map of High-Mobility Molecular Semiconductors. Nat. Mater. 2017, 16 (10), 998–1002. 10.1038/nmat4970. PubMed DOI

Mitsui C.; Okamoto T.; Yamagishi M.; Tsurumi J.; Yoshimoto K.; Nakahara K.; Soeda J.; Hirose Y.; Sato H.; Yamano A.; Uemura T.; Takeya J. High-Performance Solution-Processable N-Shaped Organic Semiconducting Materials with Stabilized Crystal Phase. Adv. Mater. 2014, 26 (26), 4546–4551. 10.1002/adma.201400289. PubMed DOI

Seki S.; Saeki A.; Sakurai T.; Sakamaki D. Charge Carrier Mobility in Organic Molecular Materials Probed by Electromagnetic Waves. Phys. Chem. Chem. Phys. 2014, 16 (23), 11093–11113. 10.1039/C4CP00473F. PubMed DOI

Honsho Y.; Miyakai T.; Sakurai T.; Saeki A.; Seki S. Evaluation of Intrinsic Charge Carrier Transport at Insulator-Semiconductor Interfaces Probed by a Non-Contact Microwave-Based Technique. Sci. Rep. 2013, 3 (1), 3182.10.1038/srep03182. PubMed DOI PMC