Hash-Mark-Shaped Azaacene Tetramers with Axial Chirality

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Hash mark-shaped Azaacene Tetramers with Axial Chirality Yuki Inoue, Daisuke Sakamaki, Yusuke Tsutsui, Masayuki Gon, Yoshiki Chujo, and Shu Seki J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b02689 • Publication Date (Web): 21 May 2018 Downloaded from http://pubs.acs.org on May 21, 2018

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Journal of the American Chemical Society

Hash Mark-shaped Azaacene Tetramers with Axial Chirality Yuki Inoue,† Daisuke Sakamaki,*,†,§ Yusuke Tsutsui,† Masayuki Gon,‡ Yoshiki Chujo,‡ and Shu Seki*,† † Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan ‡ Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan

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Abstract The tetramers of azapentacene derivatives with unique hash mark (#)-shaped structures were prepared in a quite facile manner. The #-shaped tetramers are optically active because of possessing extended biaryl skeletons, and the structure of the tetramer composed of four dihydrodiazapentacene (DHDAP) units (1) was investigated as the first example of this kind of molecule. The tetramer 1 showed characteristic chiroptical properties reflecting its orthogonally arranged quadruple DHDAP moieties, as well as redox activity. The solution of enantiopure 1 exhibited intense circularly polarized luminescence (CPL) with a dissymmetry factor of 2.5×10−3. The absolute configuration of the enantiomers of 1 was experimentally determined by X-ray crystal analysis for the dication salt of the enantiomer of 1 with SbCl6− counterions. The solutions of enantiopure 12+·2[SbCl6−] also showed NIR circular dichroism (CD) spectra over the entire range from visible to 1100 nm, enabling the modulation of the chiroptical properties by redox stimuli.


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INTRODUCTION The demands for multifunctional organic molecules have been increasing in association with a recent development of organic electronic materials and devices.

Polycyclic

aromatic hydrocarbons (PAHs) with well-defined structures, represented by pentacene1 and hexabenzocoronenes2 have been intensively studied as building blocks of multifunctional materials.

Azaacenes, which are the nitrogen-substituted analogues of

acenes, could also be important compounds because of their interplaying nature of optoelectronic properties such as photoluminescence, electronic conductivity, and redox activity.3,4 In particular, organic materials exhibiting chiroptical properties have attracted much interest for the future optical devices and molecular switches.5,6 In this context, a facile synthetic approach for constructing chiral skeletons with the planar azaacene units may open new applications of this class of compounds as multifunctional materials exhibiting chiroptical properties and other functions.7–12

Among the members of

azaacenes, 6,13-dihydro-6,13-diazapentacene (DHDAP), which corresponds to the reduced form of 6,13-diazapentacene, is a hopeful component of organic functional materials due to its ease of chemical modification by various reactions.13–18 In 2015, we reported that monoalkyl-substituted DHDAP can dimerize in the presence of 2,3dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an oxidant to give cruciform dimers



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connected via a C–N bond, which could be further induced to the double heterohelicenes by intramolecular oxidative fusion using a combination of DDQ and scandium triflate (Sc(OTf)3).17 Herein unprecedented hash mark (#)-shaped molecules were readily synthesized by the inter-molecular dimerization of the cruciform dimers.

Delicate

control of the oxidation condition caused a dramatic change from intra- to inter-molecular coupling reactions, leading to distinct chiral molecules: from double helicenes to #shaped tetramers.

Scheme 1. Synthesis of #-shaped tetramers via cruciform heteroacene dimers by tandem oxidative couplings.

RESULTS AND DISCUSSION 4 ACS Paragon Plus Environment

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Synthesis The key finding is that the cruciform dimers of monoalkyl substituted DHDAP can afford regioselective dimerization instead of intramolecular fusion by further oxidation with 0.5 equivalent of DDQ (Scheme 1).

Mass spectral data clearly indicated that the reaction of

the cruciform dimer 3 with DDQ resulted in the dimerization of 3 accompanied with the removal of two hydrogen atoms, giving the tetramer of DHDAP (Figure S1), and no peaks corresponding to the hexamer and the octamer were found.

The product was purified

by silica gel chromatography and confirmed to be single structural isomer 1.

The

oxidation of 3 with DDQ in more diluted conditions also gave the tetramer 1, and therefore the existence of Sc(OTf)3 is crucial for the intramolecular fusion of 3.19

The

tetramer 1 could be also prepared in a one-pot manner by two-step addition of DDQ to 5 without isolating 3.

Similarly, the tandem oxidation of dibenzophenoxazine 6 with

DDQ also gave the tetramer 2.

Further addition of DDQ to the tetramers gave no

reaction under the same reaction condition (Figure S2).

The tetramer 1 showed an

increased solubility to organic solvents such as CH2Cl2, toluene, acetone, and tetrahydrofuran compared with the di-propyl substituted DHDAP (5’); for example, the solubility of 1 and 5’ in CH2Cl2 were ca. 120 g L−1 and ca. 30 g L−1, respectively. On the other hand, the tetramer 2 had a lower solubility (ca. 5 g L−1 in CH2Cl2).



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X-Ray Crystal Analysis X-ray single crystal analysis revealed the structures of the tetramers 1 and 2 as shown in Figure 1 and Figure S4.

Both the tetramers 1 and 2 take unique #-shaped structures,

where the cruciform dimers are linked by a C–C bond at the unsubstituted ortho-positions of NH groups (14 position in Scheme 1).

This is in striking contrast to the dimerization

of monomers resulting in a formation of a C–N bond. Hampering of C–N coupling reaction could be due to the steric hindrance on the NH position with the largest spin density in the radical cationic state of 3. Then it is presumed that the C–C bond formation between 14 positions having the second highest spin density was preferred.

The #-

shaped tetramers are optically active molecules possessing extended biaryl skeletons,20,21 whereas their precursors are achiral molecules. The obtained crystals of 1 and 2 were racemic mixtures of two enantiomers denominated Ra (or M) and Sa (or P) isomers according to the nomenclature of other biaryl systems.

In 1, all the DHDAP planes were

almost perpendicular to the connected neighbors. For the subsequent discussions, each DHDAP plane is labeled as a, b, a’, and b’ as shown in Figure 1. are structurally equivalent; b and b’ are also equivalent.

The planes a and a’

Two pairs of cofacially arranged

DHDAP planes (a//b’ and b//a’) present in a molecule of 1.


As measures of the

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interlayer distance between cofacially arranged DHDAP units, the distances between the eclipsed C–N contacts (rC–N,inner and rC–N,outer) were introduced and indicated in Figure 1c. The values of rC–N,inner and rC–N,outer were 4.54 and 4.22 Å, respectively, with enough spaces between the units. The shortest atomic contact between the cofacial DHDAP planes was also estimated as 3.77 Å; the wider value than the typical inter-planar distances in - contact suggests that the through-space interaction between DHDAP units could be small. The packing structure of 1 was shown in Figure S5. alternate layers of (Sa)- and (Ra)-isomers.

The crystal contains

There was no significant intermolecular -

stacking.



Figure 1. X-ray crystal structures of (Sa)-1 in a racemic crystal. a) Front view and b) side view. c) Interlayer distances between of cofacially arranged DHDAP units. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are set at 50% probability.

DFT Calculations DFT calculation at B3LYP/6-31G* level was performed for 1, and the optimized structure of 1 accorded well with the one in the crystal structure. 8 ACS Paragon Plus Environment

The frontier molecular orbital

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(MO) diagram of 1 was shown in Figure 2.

The HOMO and the (HO−1)MO were

almost energetically degenerate and these two MOs were distributed on the outer two DHDAP units (a and a’). The (HO−2)MO was located energetically lower than the degenerate HOMOs by 72 meV, and the (HO−3)MO was lower than the (HO−2)MO by 62 meV. These two MOs were localized on the inner two DP units (b and b’).

The split

of the (HO−3)MO and the (HO−2)MO suggests the small but non-zero electronic communication between the inner two DHDAP units connected by the C–C bond. These four occupied MOs were energetically close to each other, reflecting the molecular structure of 1 having four segmented electron donor units.

In contrast, the four

unoccupied MOs were composed of two pairs of quasi-degenerate MOs: the LUMO and the (LU+1)MO distributed on the inner two DHDAP units (b and b’), and the (LU+2)MO and the (LU+3)MO distributed on the outer two DHDAP units (a and a’). These results indicate that the electronic environments of DHDAP units can be classified into the inner and the outer pairs of DHDAPs.



Figure 2. Frontier MOs of 1 (B3LYP/6-31G*).

Electrochemistry The results of electrochemical measurements (cyclic voltammetry and differential pulse voltammetry) of the tetramer 1 were summarized in Table 1 with the reference values


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observed for the dimer 3 and 5’ (for the voltammograms see Figure S9–S11).

The first

oxidation potential of 1 was almost identical as that of the dimer 3 but the second oxidation was slightly lower than that of 3. Additionally, 1 showed one simultaneous two-electron oxidation at the relatively low potential (0.308 V vs. Fc0/Fc1+), following the first two oxidation processes. The observed four-electron oxidation of 1 could be attributed to the four one-electron removals from each DHDAP unit, judging from the frontier MO diagrams and the large potential difference between the first and the second oxidation (ΔE = E2 − E1) of 5’ (550 mV).

In the dicationic state of 1, the positive charges

(and the radical spins) are localized on the outer two DHDAP units to minimize the electrostatic repulsion considering the MO distributions of the degenerate HOMOs.

Table 1. Oxidation potentials (V vs. Fc0/Fc1+) of 1, 3, and 5’ in CH2Cl2 (0.1 M nBu4NBF4). E1

E2

E3

1

0.037

0.142

3

0.038

0.165

0.127

5’

0.011

0.561

0.550

ΔE [a]

0.308

[a]Quasi-two-electron transfer process.


0.105


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Photophysical Properties Figure 3 shows the absorption and photoluminescence spectra of 1, 3, and 5’ in CH2Cl2. The absorption spectral shape of 1 was slightly different from the almost overlapped ones in 3 and 5’. The absorption band around 420 nm of 1 splits into a vibronic progression pattern with a longer wavelength shoulder (432 nm). The difference of the spectral shape of 1 could be explained by the superposition of the optical transitions of outer (a and a’) and inner (b and b’) DHDAP units with respective vibronic states.

The observed

shoulder at the longer wavelength (432 nm) were attributed predominantly to the transitions of the inner two DHDAP moieties with the lower LUMO levels by the TDDFT calculations (Figure S14 and Table S6). The fluorescence spectrum of 1 red-shifts slightly relative to those of 3 and 5’ due to the formation of the C–C bond between the two DHDAP units.

The 0→0

transition was the largest in the vibronic pattern of the emission band of 1, whereas the 0→1 transition was the largest in those of 3 and 5’.

This suggests that the structural

relaxation in the S1 state of 1 is more restricted due to its interlocked structure compared with 3 and 5’.

The emission quantum yield of 1 (f = 0.47) was as high as those of 3

(f = 0.38) and 5’ (f = 0.43). This is in contrast to the drastically reduced emission quantum yields of the double N-heterohelicenes made by the oxidative fusion of the


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cruciform dimers of DHDAP (f < 0.05).17 No excimer emission or emission quenching were observed for 1, also suggesting the small interlayer interaction between the cofacially aligned DHDAP planes separated by longer than 4 Å on average.

No

significant differences were found in the decay profiles of the fluorescence of 1, 3, and 5’ (Figure S16).



Figure 3. a) Absorption and b) emission spectra of rac-1, 3, and 5’ in CH2Cl2.

Chiroptical Properties of 1


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Two enantiomers of 1 were successfully separated using a high-performance liquid chromatography system with a chiral stationary phase (Figure S19).

The absolute

configurations of the first/second eluted fractions are identified experimentally as (Ra)and (Sa)-isomers, respectively, by single crystal X-ray analysis of corresponding dication salts as described in a later part.

Figure 4a shows the circular dichroism (CD) spectra of

two enantiomers of 1 in CH2Cl2 solution.

The (Sa)- and (Ra)-isomers gave a positive and

a negative Cotton effect at their lowest energy bands, respectively. This is similar to the case of 5,5’-bitetracene, which is the carbon analogue of the inner DHDAP pairs of 1,20 being in accordance with the prediction by the exciton chirality method.22

The observed

CD spectral pattern was also in accordance with the simulated pattern based on the TDDFT calculations (Table S11 and Figure S24). Encouraged by the high fluorescence quantum yield of 1, circular polarized luminescence (CPL) spectra were measured for (Sa)- and (Ra)-isomers of 1.

As shown in Figure 4b, the enantiomers showed clear CPL

spectra of mirror images of each other. The dissymmetry factor for the CPL (|gCPL|) was relatively high 2.5×10−3 (at 442 nm) for organic fluorophores.23–34



Figure 4. a) CD spectra of the enantiomers of 1 in CH2Cl2 at 298 K. b) CPL spectra of the enantiomers of 1 in CH2Cl2 (3.0×10−6 M). Excitation wavelength was 300 nm.


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Structure Elucidation of 12+ Determination of the absolute configuration of chiral compounds is very important for discussing the relationship between the structure and chiroptical properties but often the most taxing steps.

In general, X-ray anomalous scattering effects cannot be expected

for the determination of the absolute configurations of molecules without heavy atoms like 1, and therefore, introduction of heavy atoms by chemical modification, such as bromination, is often the choice to lead the anomalous dispersion.35,36

In this work,

heavy atoms were successfully introduced into a crystallite based on the stable redox activity of 1.

Enantiopure cations of 1 were isolated by chemical oxidation with tris(4-

bromophenyl) aminium hexachloroantimonate (Magic Blue)37 containing heavy atoms in its anionic part of SbCl6−.11

Fortunately, the dication salt of the secondary eluted isomer

in the chiral HPLC separation ((+)-1) was successfully obtained as single crystals suitable for X-ray analysis by oxidation with 2 equivalent of Magic Blue.

X-ray analysis

confirmed that the crystal belonged to a chiral space group orthorhombic P21212 and contained the dications of (Sa)-1 (Flack parameter = −0.026(15)).

Similar to its neutral

state, 12+ held a #-shaped structure and the two pairs of cofacially arranged DHDAP units (a//b’ and b//a’ in Figure 5b) were crystallographically equivalent.

Notably, the

interlayer distances between a//b’ and b//a’ became closer compared with the neutral



state; the distances of rC–N,inner and rC–N,outer, decreased from 4.54 and 4.22 (1) to 4.42 and 3.69 Å (12+),

respectively, and the shortest atomic contact between the DHDAP units

also decreased from 3.77 (1) to 3.56 Å (12+), suggesting the existence of attractive interactions between the cofacial DHDAP planes in 12+.

This suggests that the two

positive charges (and spins) are distributed one by one to the two pairs of cofacially arranged DHDAP planes in 12+, resulting in the attractive interactions between the cofacial DHDAP planes due to the resonance stabilization in analogy to -dimer cation complexes composed of two planar -systems sharing a positive charge and a spin.38 As shown in Figure S6, 12+ formed one-dimensional arrays along c-axis and each array was surrounded with counter anions and solvent molecules.


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Figure 5. X-ray crystal structures of (Sa)-12+·2[SbCl6−]. a) Packing structure, b) front view of 1, and c) Interlayer distances between of cofacially arranged DHDAP units. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are set at 50% probability.



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Chiroptical Properties of 12+ Figure 6a shows the UV-Vis-NIR absorption spectra of 12+·2[SbCl6−] in CH2Cl2.

In

addition to the absorption bands around 300 and 410 nm observed also in the neutral state, the dication 12+ showed new absorption bands in the visible region ranging from 450 to 700 nm as well as weak bands in the NIR region up to 1300 nm.

The observed spectrum

of 12+ was well reproduced by TD-DFT calculations (Figure S20 and S21).

Next, the

CD spectra of the solutions of (Sa)- and (Ra)-12+·2[SbCl6−] were recorded as the mirror imaged ones over the UV to NIR region9a,12,39,40 (Figure 6b, c). The simulated CD spectra based on the TD-DFT calculations for (Sa)- and (Ra)-12+ matched qualitatively in sign of Cotton effects observed for the corresponding isomers (Table S12 and Figure S25).

The

CD signals in the NIR region are also suggested to be partly due to the intramolecular charge transfer transitions among the DHDAP moieties.


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Figure 6. a) UV-Vis-NIR spectrum of (Ra)-12+·2[SbCl6−] in CH2Cl2. b) and c) CD spectra of (Sa)- and (Ra)-12+·2[SbCl6−] in CH2Cl2 (6.0×10−6 M for b and 8.5×10−5 M for c).



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Electron Spin Resonance of 12+ To investigate spin-spin interaction in 12+, whether a diradical dication or a closed-shell dication, we measured the ESR spectra of rac-12+·2[SbCl6−] (Figure S22 and S23).

The

solution of rac-12+·2[SbCl6−] in CH2Cl2 showed a broad and intense ESR signal at 293 K, showing its diradical character.

The frozen solution of 12+ at 123 K gave an intense ESR

signal; no forbidden transition nor fine structure characteristic of spin triplet states were observed. This is due to the large separation between two radical spins localized on the outer two DHDAP moieties (a and a’), as expected by the frontier MO distribution.

CONCLUSIONS In this work, we have succeeded in synthesis and characterization of the #-shaped azaacene tetramers with axial chirality. These tetramers were obtained by a facile way of successive oxidative coupling reactions starting from simple azaacene derivatives in onepot procedures.

The tetramer 1 composed of four DHDAP moieties exhibited

chiroptical and electrochemical properties reflecting its quadruple donor structure connected orthogonally to each other.

The two enantiomers of 1 were successfully

separated, and the enantiomers exhibited CPL activity with a relatively high quantum yield and dissymmetry factor |gCPL| > 10−3.

The absolute configuration of the


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enantiomers of 1 was determined by single X-ray analysis for the dication salt of an isomer with SbCl6− counter anions. Both the solutions of (Sa)- and (Ra)-12+·2[SbCl6−] showed CD spectra over a broad wavelength range from UV to NIR. dication nature of 12+ was confirmed by the ESR measurements.

The diradical

The results presented

herein could provide new applications of azaacene families as multifunctional materials with chiroptical properties by the demonstrated dense but exquisite spatial arrangement of the molecular motifs in addition to the other electronic properties originated from azaacenes.

ASSOCIATED CONTENT

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/ XXXXXX. Crystallographic data for 1 (CIF) Crystallographic data for 12+·2[SbCl6−] (CIF) Crystallographic data for 2 (CIF) Crystallographic data for 3 (CIF) 23 ACS Paragon Plus Environment


Crystallographic data for 5’ (CIF)

Details of synthesis and characterization (NMR, MALDI-MS, and HRMS), details of optical resolution, X-ray structural data, DFT calculations, CV, UV-Vis-NIR, ESR, and CD spectra (PDF)

AUTHOR INFORMATION

Corresponding Author [email protected] [email protected] Present Address §

D.S: Department of Chemistry, Graduate School of Science, Osaka Prefecture

University, Naka-ku, Sakai-shi, Osaka 599-8531, Japan, [email protected] ORCID Daisuke Sakamaki: 0000-0001-6503-1607 Shu Seki: 0000-0001-7851-4405 Notes The authors declare no competing financial interest. 24 ACS Paragon Plus Environment

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ACKNOWLEDGMENT

This work was supported by a Grant-in-Aid for Young Scientists (A) (17H04874) from the Japan Society for the Promotion of Science (JSPS) and a Grant-in-Aid for Scientific Research on Innovative Areas (“-System Figuration” Area, 26102011). The theoretical calculations were performed using Research Center for Computational Science, Okazaki, Japan.

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TOC Graphic


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Hash-Mark-Shaped Azaacene Tetramers with Axial Chirality

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