Letter Cite This: Org. Lett. 2018, 20, 1409−1412
pubs.acs.org/OrgLett
Carbonyl-Functionalized Cyclazines as Colorants and Air-Stable n‑Type Semiconductors Artem Skabeev,§ Ute Zschieschang,‡ Yulian Zagranyarski,§ Hagen Klauk,*,‡ Klaus Müllen,*,†,± and Chen Li*,† †
School of Environment and Civil Engineering, Dongguan University of Technology, No.1, Daxue Rd., Songshan Lake, Dongguan, Guangdong Province People’s Republic of China § Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany ± Institute of Physical Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany ‡ Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart, Germany S Supporting Information *
ABSTRACT: A series of π-extended cycl[3,3,2]azines (3) bearing additional carbonyl groups were synthesized via aldol condensations. Two strong electron acceptor molecules (4 and 5), with low-lying LUMO energy levels of −3.99 and −3.95 eV, respectively, were obtained. Organic thin-film transistors (TFTs) based on the cyanated cyclazine derivatives 5 were fabricated by vapor deposition, exhibiting extraordinarily stable n-type semiconductor character under ambient condition with the highest electron mobility of 0.06 cm2 V−1 s−1 consistently for more than 30 months.
R
(Scheme 1), like other carbonyl-based chromophores, reveals pronounced colorant properties.10 Furthermore, the strong
ecently, nitrogen doping of carbon materials such as nanodiamonds and graphenes has gained increasing attention.1,2 Cyclazines I−III, where the nitrogen is located in the center of a tricyclic conjugated π-system, represent the smallest possible cutout of N-graphenes. The term cyclazines was introduced by Boekelheide et al.; thereby, cycl[3,2,2]azine (I), cycl[3,3,3]azine (II) and cycl[3,3,2]azinium cation (III) (see Figure 1) are known as the most popular examples.3−5
Scheme 1. Synthesis of Compounds 1, 2, 3, 4, and 5
Figure 1. Structures of cyclazines.
Cyclazines can also be described as N-bridged annulenes with three different bonding situations at the N atom, yielding a pyrrolic (I), pyridinic (II), or quaternary (III) center. However, despite their attractive chemical, physicochemical, and magnetic properties, difficult synthetic routes to cyclazines have somehow hampered further studies.6−9 Herein, for the first time, we describe the synthesis and characterization of carbonyl-functionalized cyclazines. With two CO groups as auxochromic units, diketocycl[3,3,2]azine 3 © 2018 American Chemical Society
Received: January 18, 2018 Published: February 15, 2018 1409
DOI: 10.1021/acs.orglett.8b00183 Org. Lett. 2018, 20, 1409−1412
Letter
Organic Letters
5a′ exhibits a slip angle of ∼120°. Nevertheless, both crystals show a staircase-type assembly in the crystal structures (Figure 2, c-axis view of the crystals 3a′ and 5a′). Wide-angle X-ray scattering (WAXS) of the dried powders of 4a′, 5a′, and 5b (see the Supporting Information) confirmed the presence of similar packing modes. Cyclic voltammetry was performed on all cyclazines 3−5. The redox potentials and the estimated lowest unoupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energies are summarized in Table 1. All cases exhibit two reversible reduction waves (due to the two carbonyl groups), but only one oxidation wave (corresponding to the N atom) within the accessible potential range in CH2Cl2. The LUMO level decreases as the number of cyano substituents is increased. 3a (no cyano), 4a (two cyano groups), and 5a (four cyano substituents) made via phthalic anhydride revealed LUMO levels of −3.37, −3.72, and −3.99 eV, respectively. While 3b, 4b, and 5b, containing zero, two, and four cyano groups, respectively, showed LUMO levels of −3.33, −3.69, and −3.95 eV. Obviously, increasing the conjugation system from a (benzene) to b (naphthalene) has a minor effect on the molecular LUMO levels. Since the LUMO levels of cyclazines 5a and 5b are close to −4 eV, they appear as candidates for the fabrication of air-stable n-channel thin-film transistors (TFTs). Cyclazines 3−5 fail to show fluorescence. Their ultraviolet− visible light (UV-vis) absorption spectra measured in CH2Cl2 are displayed in Figure 3. 3 is yellow with an absorption maximum at ∼445 nm, 5a and 5b are blue with λmax = 629 and 621 nm, respectively, indicating, again, only a weak influence of the core extension from benzene to naphthalene. On the other hand, in the solid state, all cyclazines 3a′, 4a′, and 5a′ reveal a golden metallic luster (see their powder pictures in the Supporting Information). The TFTs based on 5a and 5b were fabricated in the bottom-gate, top-contact architecture, using a heavily doped silicon wafer as the substrate and gate electrode. The gate dielectric is a combination of a 100-nm-thick layer of thermally grown silicon dioxide, an 8-nm-thick layer of aluminum oxide grown by atomic layer deposition, and a self-assembled monolayer of n-tetradecylphosphonic acid.14 During the semiconductor deposition, the substrate was held at a temperature of 140 °C. For the source and drain contacts, gold was deposited via thermal evaporation in vacuum and patterned using a shadow mask. The channel length is 100 μm and the channel width is 200 μm. The current−voltage measurements were performed in ambient air. The TFTs based on 5a have an electron mobility of 0.02 cm2/(V s) immediately after fabrication and 0.006 cm2/(V s) after 30 months in air (Figure 4, top row). For 5b, the electron mobility is 0.06 cm2/ (V s) both after fabrication and after 30 months in air (Figure 4, bottom row), reflecting a truly remarkable stability of the devices. Such a durability of TFTs is quite rare. Indeed, organic n-type materials have been intensively studied with a focus on charge carrier mobilities, while the critical factors for practical applications such as shelf life and operational lifetime have been set aside. The mobilities of most organic n-type semiconductorbased TFT devices often decrease after prolonged storage (literature reported stability values so far are given for 100 days at the most) in ambient atmosphere.12 A case closely related to cyclazines are perylene tetracarboxdiimides PDI-FCN2 carrying electron-withdrawing substituents whose devices display an almost 30% decrease of electron mobilities after three years.13
electron acceptor 5 serves as n-type semiconductors in TFTs with high air stability. The title system (3) was synthesized using an optimized aldol condensation protocol that was recently developed in our group.11 Using commercially accessible phthalic anhydride (a) or 2,3naphthalenedicarboxylic anhydride (b) as starting materials, cyclazine 3 was obtained via a three-step reaction. Considering that 2,6-diacetylaniline is not easily available and its reaction with anhydrides is accompanied by several byproducts, the initial imidization was performed between anhydrides a/b and 4-propyl-2,6-dibromoaniline in acetic acid under reflux conditions, leading to 1a and 1b in yields of 48% and 69%, respectively.11 Subsequent Stille coupling was conducted in 1,2dioxane at 100 °C for 12 h, furnishing acetyl derivative 2a. The most critical step, the aldol condensation, was carried out using imidazole as a solvent at 120 °C for 2 h, giving 3a in 72% yield and 3b in 83% yield. In order to test the reactivity of the carbonyl groups in 3, malononitrile was reacted with 3 under Knoevenagel conditions under acidic conditions. The yields of the 2-fold condensation are much improved if the reactants are well solubilized. In this case, when R is a tert-butyl group, 5a′ was obtained in 70% yield after purification. The structures of all new compounds were confirmed by 1H NMR, 13C NMR, and HRMS or elemental analysis (see the Supporting Information). Single crystals of 3a′ and 5a′ were obtained by slow diffusion of hexane into CH2Cl2 solutions. As shown in Figure 2, both 3a′ and 5a′ have a planar conjugated core structure. 3a′ possesses an almost-perfect head-to-tail parallel arrangement between two neighboring molecules, while
Figure 2. Crystal structures of 3a′ and 5a′: (a) top view and (b) side view. Columnar packing diagram along (c) the b-axis and (d) the caxis. 1410
DOI: 10.1021/acs.orglett.8b00183 Org. Lett. 2018, 20, 1409−1412
Letter
Organic Letters Table 1. Absorption and Electrochemical Properties of 3a−5b 3a 4a 5a 3b 4b 5b
ε0a (M−1cm−1)
λmax (nm)
Eredb (V)
Eoxb (V)
Eg (eV)
HOMOc (eV)
LUMOd (eV)
29 200 41 500 79 500 27 600 38 300 73 800
449 553 629 441 547 621
−1.43 −1.08 −0.81 −1.47 −1.11 −0.85
1.26 1.18 1.12 1.16 0.96 0.97
2.69 2.26 1.93 2.63 2.07 1.82
−6.06 −5.98 −5.92 −5.96 −5.76 −5.77
−3.37 −3.72 −3.99 −3.33 −3.69 −3.95
Measured at λmax. bOnset potentials, determined by cyclic voltammetric measurements in 0.1 M solution of Bu4NPF6 in CH2Cl2 vs Fc+/Fc. Estimated vs vacuum level from EHOMO = −4.80 eV − Eox. dEstimated vs vacuum level from ELUMO = −4.80 eV − Ered..
a c
materials, such as pyromellitic dianhydride or 2,3,6,7naphthalene dianhydride, are in progress.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.orglett.8b00183. Full experimental details and characterization data (PDF)
Figure 3. UV-vis absorption of 3a, 4a, and 5a (left panel) and 3b, 4b, and 5b (right panel) in CH2Cl2.
Accession Codes
CCDC 1817712−1817713 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
[email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.; fax: +44 1223 336033.
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AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected] (H. Klauk). *E-mail:
[email protected] (K. Müllen). *E-mail:
[email protected] (C. Li). ORCID
Klaus Müllen: 0000-0001-6630-8786 Chen Li: 0000-0002-8438-259X Author Contributions
The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes
The authors declare no competing financial interest.
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Figure 4. Measured current−voltage characteristics of n-channel thinfilm transistors (TFTs) based on 30 nm-thick, vacuum-deposited layers of 5a (top row) and 5b (bottom row) as the semiconductor.
ACKNOWLEDGMENTS We cordially thank Dr. Dieter Schollmeyer (Institute of Organic Chemistry, Johannes Gutenberg University Mainz) for X-ray crystal structure analysis. We also thank Dr. Florian Ernst Golling and Mrs. Filiz Karagöz (Synthetic Chemistry Research Group, Max Planck Institute for Polymer Research) for fruitful discussions. K.M. is grateful for funding by the Johannes Gutenberg-Universität Mainz (JGU) through the Gutenberg Forschungskolleg Fellowship (GFK).
In conclusion, two cyclazine-based carbonyl chromophores 3a and 3b were synthesized by way of aldol condensations. The carbonyl groups of 3 were further functionalized with malononitrile to form tetracyano-substituted cyclazine derivatives 5a and 5b as deep blue chromophores with molar absorption coefficients close to 80 000 M−1 cm−1. The product 5b features high planarity, dense packing in the solid, and short interplanar distances, and it exhibits a consistent electron mobility (μ) of 0.06 cm2/(V s) for more than 30 months. Therefore, the new cyclazines 3, 4, and 5 can be used not only as colorants, but also as n-type semiconductors for practical applications. Further studies based on symmetric starting
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REFERENCES
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DOI: 10.1021/acs.orglett.8b00183 Org. Lett. 2018, 20, 1409−1412
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DOI: 10.1021/acs.orglett.8b00183 Org. Lett. 2018, 20, 1409−1412
