O,O -Disubstituted N,N -Dihydroxynaphthalenediimides (DHNDI): First principles-designed organic building blocks for materials science

Transcription

1 , -Disubstituted N,N -Dihydroxynaphthalenediimides (DHNDI): First principles-designed organic building blocks for materials science Eric Assen B. Kantchev [a] *, Huei Shuan Tan, [a] Tyler B. Norsten [a] * Michael B. Sullivan [b] a Institute of Materials Research and Engineering, A*STAR, 3 Research Link, Singapore b Institute of High Performance Computing, A*STAR, 1 Fusionopolis Way #16-16, The Connexis, Singapore kantcheveab@imre.a-star.edu.sg; norstent@imre.a-star.edu.sg Contents Page 1. DFT computational studies S2 2. Experimental materials and methods S25 3. Synthetic procedures S26 4. NMR Spectra S29 5. Additional surface characterization for compd. 12 S32 6. Solid state UV and TFT device characterization S32 7. References S33 S 1

2 1. DFT computational studies 1.1. Computational methodology All computations were performed on Gaussian 09 (AM64L -G09RevA.02) 1 and Gaussview 5.1W as GUI using default M06 DFT functional and DGTZVP basis set in gas phase or implicit solvent (dichloromethane) by SMD treatment. ptimizations were performed from structures built in Gaussview via pre-optimization at HF/3-21g at M06/DGTZVP first in gas phase, then in implicit solvent with cutoff values for Maximum Force = , RMS Force = , Maximum Displacement = , RMS Displacement = All optimized structures were confirmed to reside in their respective PEHS minima by having only positive vibrational frequencies Table 1-SI (extended version of Table 1 in the manuscript) Table 1-SI. Computational (DFT) characterization of -functionalized DHNDI derivatives at M06/DGTZVP levels of theory in gas phase and in CH 2 Cl 2 under the dispersion-corrected polarized continuum implicit solvation model (SMD). Gas phase CH 2Cl 2 G G A B C (kcal HM/LUM (kcal HM/LUM D1, D2, mol - D1, D2, (ev) mol -1 ) (ev) 1 ) 3a a / / b CH 2 CH 2 CH / / c / / a a / / b CH 2 CH / / c / / a a / / b C= CH / / c / / a a / / b C= CF / / c / / a a / / b C= N(CH 3) / / c / / a a / /-3.51 =S= CH 3 8b / /-3.51 a Chosen as the reference structure. S 2

3 1.3. Structure plots, Cartesian coordinates SCF convergence and thermochemistry data for all structures in Table 1 at SMD (CH 2 Cl 2 )/M06/DGDZVP level of theory Structure 1(gas phase) SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 2 (gas phase) S 3

4 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 3a S 4

5 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 3b S 5

6 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) S 6

7 Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 3c S 7

8 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 4a S 8

9 SCF Done: E(RM06) = A.U. after 2 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 4b S 9

10 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 4c S 10

11 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 5a S 11

12 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 5b S 12

13 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 5c S 13

14 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 6a S 14

15 SCF Done: E(RM06) = A.U. after 9 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 6b S 15

16 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 6c S 16

17 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 7a S 17

18 SCF Done: E(RM06) = A.U. after 2 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= S 18

19 Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 7b S 19

20 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 7c S 20

21 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 8a S 21

22 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 8b S 22

23 SCF Done: E(RM06) = A.U. after 1 cycles Convg = D-08 -V/T = SMD-CDS (non-electrostatic) energy (kcal/mol) = (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Structure 11 (B3LYP/DGDZVP) S 23

24 SCF Done: E(RB3LYP) = A.U. after 1 cycles Convg = D-08 -V/T = S 24

25 (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= HM and LUM contour plots for selected structures 2. Experimental materials and methods. All solvents and reagents used in the synthetic schemes were used as received except where noted. 1 H and 13 C spectra were recorded on a Bruker 400 MHz spectrometer. Chemical shifts were referenced to tetramethylsilane (0.00 ppm). Low and high resolution mass spectra data was acquired at the National University of Singapore Mass Spectrometry Laboratory. Cyclic voltammetry measurements of compounds were carried out under nitrogen atmosphere using an AUTLAB model PGSTAT30 workstation with 0.1 M tetra-n-butylammonium hexafluorophosphate as supporting S 25

26 electrolyte in freshly distilled and degassed CH 2 Cl 2 using platinum foil working electrode, a gold counter electrode and a silver/silver chloride reference electrode. Fc/Fc+ was used as internal reference for all measurements. The scan rate was 50mV s -1. All solutions for cyclic voltammetry were thoroughly purged with N 2 before the CV measurements. UV-Vis data were recorded on a Shimadzu UV-Vis-NIR 3101 PC scanning spectrophotometer. The thin film samples for XRD measurements were deposited on the TS-modified Si 2 /Si substrate by thermal evaporation with LED heating source in a alumina crucible. Prior to deposition, 11 and 12 were purified via sublimation. Thin films (~67 nm of 11 and ~ 65 nm of 12) were evaporated at 120 and 115 C, respectively, under a base pressure of mbar; at substrate temperature of 60 C, and deposition rates of 0.5 Å/s. The thin films morphology was characterized in tapping mode by using multimode Atomic Force Microscopy. The AFM scans were performed both in ambient condition using scan size of 5 m and a scan rate of 1Hz. The crystallinity of 11 and 12 was determined by using XRD patterns and were obtained on an Analytical X PERT PR system using Cu Kα source (λ= Å) in air over 2θ range of 2 to Synthetic procedures 2,7-Dihydroxybenzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (DHNDI) (2): Naphthalene[1,8:4,5]tetracarboxylic acid dianhydride (9) (6.71 g, 25 mmol) and NH 2 H HCl (3.47 g, 50 mmol) were suspended into freshly-distilled, amine-free DMF (50 ml) and n-bu 3 N (12 ml, 9.30 g, 50 mmol) were syringed in over 10 min with vigorous stirring, whereupon the yellow suspension thickened and changed color to offwhite. The mixture was heated with stirring at 140 C for 1 h in an open flask. During that time, the initial off-white precipitate dissolved and then bright yellow, fine-crystalline precipitate of 2 appeared. The mixture was cooled to room temperature, diluted with CH 3 CN (50 ml), filtered and the filter cake washed with CH 3 CN (4 15 ml), followed by copious amounts of diethyl ether. The powder was transferred into a pre-weighed roundbottomed flask and was heated under high vacuum at 100 C for 2 h with frequent S 26

27 shaking and turning of the solid around to ensure all solvents have been completely removed. The known compound 2 2 (6.63 g, 89 %) was isolated as a bright yellow solid. 1,3,6,8-Tetraoxobenzo[lmn][3,8]phenanthroline-2,7(1H,3H,6H,8H)-diyl di-n-hexanoate (, -Di-n-hexanoylDHNDI) (10) : Compound 2 (0.447 g, 1.5 mmol) and DMAP (0.009 g, 5 mol%, mmol) were suspended in dry CHCl 3 (15 ml) and n-hexanoyl chloride (0.47 ml, g, 3.3 mmol) and n-bu 3 N (0.79 ml, g, 3.3 mmol) were added via syringe in succession. The mixture was stirred in ambient temperature over 18 h, the volatiles were removed in vacuum and the residue was suspended in CH 3 CN (10 ml). The precipitate was filtered, washed with CH 3 CN (3 2 ml) and dried thoroughly with a stream of air. Compound 10 (550 mg, 74 %) was obtained as a white solid. 1 H NMR (CDCl 3 ): 8.83 (s, 4H), 2.76 (t, 4H, J = 7.6 Hz), 1.86 (m, 4H), (m, 8H), 0.98 (t, 3H, J = 7.2 Hz); 13 C NMR (CDCl 3 ): 169.9, 158.3, 132.2, 127.5, 127.0, 31.5, 31.4, 24.8, 22.6, 14.3; HRMS (ESI): m/z (M - ); Calcd for C 26 H 26 N 2 8 : ,3,6,8-Tetraoxobenzo[lmn][3,8]phenanthroline-2,7(1H,3H,6H,8H)-diyl dipivalate (, -DipivaloylDHNDI) (11) : Following the procedure for 10, from 2 (0.596 g, 2.0 mmol), DMAP (0.012 g, 5 mol%, mmol), CHCl 3 (20 ml), pivaloyl chloride (0.62 ml, g, 5.0 mmol) and n-bu 3 N (1.20 ml, g, 5.0 mmol) compound 11 (722 mg, 77 %) was obtained as a white solid. 1 H NMR (CDCl 3 ): 8.81 (s, 4H), 1.51 (s, 18H); 13 C NMR (CDCl 3 ): 174.4, 158.5, 132.0, 127.6, 127.0, 39.0, 27.5; HRMS (ESI): m/z (M - ); Calcd for C 24 H 22 N 2 8 : S 27

28 2,7-Bis(n-hexyloxy)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (, - Di-n-hexylDHNDI) (12): Under Ar, 2 (0.596 g, 2.0 mmol) and PPh 3 (1.31 g, 5.0 mmol) were suspended in dry, air-free DMF (5.7 ml). 1-Hexanol (0.63 ml, g, 5.0 mmol) and 50 vol% solution of DEAD in toluene (2.30 ml, g DEAD, 5.0 mmol) was added drop-wise via syringe over 10 min. Addition of DEAd resulted in dark-brown mixture, which turned gray within 30 min. The misture was stirred for 3 h, the volatiles were removed in vacuo and the residue was suspended in CH 3 CN (10 ml). The precipitate was filtered, washed with CH 3 CN (3 2 ml) and dried thoroughly with a stream of air. Compound 12 (741 mg, 79 %) was obtained as a white solid. 1 H NMR (CDCl 3 ): 8.80 (s, 4H), 4.27 (t, 4H, J = 6.8 Hz), 1.87 (m, 4H), 1.54 (m, 4H), 1.37 (m, 8H), 0.92 (t, 3H, J = 6.4 Hz); 13 C NMR (CDCl 3 ): 160.0, 131.8, 127.7, 126.6, 79.9, 32.0, 28.5, 25.8, 22.9, 14.4; HRMS (ESI): m/z (M - ); Calcd for C 26 H 30 N 2 6 : S 28

29 4. NMR spectra N N 10 N N 10 S 29

30 N N 11 N N 11 S 30

31 N N 12 N N 12 S 31

32 5. Additional surface characterization of compound 12 Figure 1-SI. XRD intensity graph and AFM height (left inset) and phase (right inset) images of a spin cast film (CHCl 3 ) 12 on TS-modified Si/Si 2 substrate. 6. Solid State UV & TFT Device Characterization Figure 2-SI. UV-Vis spectra of an evaporated film (thickness ~ 40nm) of DHNDI 11 on quartz substrate. The thin film transistor properties of 11 as a channel semiconductor was evaluated using a bottom-gate, top-contact TFTs configuration. Heavily p-doped silicon wafer with a layer of ~200 nm (17.25 nf cm -2 ) Si 2 on the surface was used as the substrate. Sublimed grade of 11 was thermally evaporated at C ( thickness ~50-70 nm) on a octyltrichlorosilane (TS-8) pretreated substrate under a base pressure of mbar with substrate temperature maintained at room temperature, and the deposition rates was S 32

33 controlled at 0.5 /s. A pair of Au electrodes was then thermally evaporated to act as source and drain. The TFT devices were then characterized using a Keithley SCS-4200 probe station under an ambient environment with relative humidity level of 65 % in the dark. Figure 3-SI. The top schematic shows the typical bottom gate top contact device structure used in device evaluation. (Left) utput characteristics and (right) transfer characteristics of the TFT devices measured under ambient which show no obvious transistors signal. Four devices were evaluated all showing similar characteristics as described above. Devices were also measured under nitrogen atmosphere and the same experiment was repeated for compound 12 with similar results. Spin coated devices of 11 and 12 were also prepared and showed similar output and transfer characteristics as described above. 7. References 1. Gaussian 09, Revision A.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; gliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev,.; Austin, A. J.; Cammi, R.; Pomelli, C.; chterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; rtiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, Zhong, C.-J.; Kwan, W. S. V.; Miller, L. L. Chem. Mater. 1992, 4, S 33