1,3-Diylideneisoindolines: Synthesis, Structure, Redox, and Optical

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1,3-Diylideneisoindolines: Synthesis, Structure, Redox, and Optical Properties Yuriy V. Zatsikha, Briana R. Schrage, Julia Meyer, Victor N. Nemykin, and Christopher J. Ziegler J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00468 • Publication Date (Web): 25 Apr 2019 Downloaded from http://pubs.acs.org on April 26, 2019

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The Journal of Organic Chemistry

1,3-Diylideneisoindolines: Synthesis, Structure, Redox, and Optical Properties Yuriy V. Zatsikha,† Briana R. Schrage,‡ Julia Meyer,‡ Victor N. Nemykin,*† Christopher J. Ziegler*‡ † Department

of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada of Chemistry, University of Akron, Akron, Ohio 44312-3601, United States

‡ Department

[email protected], [email protected]

ABSTRACT: Diiminoisoindoline (DII) is a crucial reagent for the synthesis of phthalocyanine as well as related macrocycles and chelates such as hemiporphyrazine and bis(iminopyridyl)isoindoline. In this report, we present the synthesis and characterization of four 1,3-diylideneisoindolines prepared via the reaction of several organic CH-acids and DII. These orange or red compounds exhibit intense →* transitions in the UV-visible region. The redox properties and electronic structures of all new compounds were investigated using cyclic voltammetry and Density Functional Theory (DFT). The observed electrochemistry and UV-visible transitions are in good agreement with the DFT and time-dependent DFT (TDDFT) calculations, which indicate that the HOMO is largely centered at the O=C-C-C=O fragments and the LUMO is more extended onto the isoindoline unit.

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Introduction 1,3-Diiminoisoindoline (DII, Scheme 1) has long been an important reagent for the synthesis of chelates and chromophores.1-5 First introduced by Linstead in the early 1950s and produced by the reaction of ammonia with phthalonitrile,5 DII can be used to synthesize phthalocyanines as well the related hemiporphyrazines, bis(arylimino)isoindoline chelates, and related chromophores.6-21 One of the most common types of reactivity observed with DII is the formation of Schiff bases upon exposure to primary amines, which is exemplified in the hemiporphyrazines and bis(arylimino)indoline ligands. However, the DII unit can potentially undergo a variety of chemical reactions to potentiate its use as a building block for a variety of structural motifs. This chemistry, outside of the well-known Schiff base chemistry, has been generally unexplored. However, this chemistry could provide a route for generating more complex molecular architectures. One example of such as reaction was explored by Lever and coworkers, who exploited the ring expansion reaction of DII with hydrazine to form phthalazines as a means to generate metal chelating compounds.22-27 In this report, we present a study into the use of organic CH-acids to prepare 1,3-diylideneisoindolines (DII, Scheme 1) from DII. Although several similar chromophores originated from the reaction between DII and organic CH-acids are reported in the patent literature28-34 and commercially available as yellow or orange pigments, their general spectroscopic, redox, and electronic structure properties are yet to be reported. In order to fill this knowledge gap, we synthesized four new compounds 1-4 as shown in the Scheme 1 using a one-step reaction between DII and organic CH-acids chosen from four different organic CH-acids: cyanoethylacetate (1), Meldrum’s acid (2), 1,3-indanedione (3), and dimethyl barbituric acid (4). Compounds 1-4 exhibit intense UV-visible bands which are highly dependent on the identity of the substituents at the alkene bridging positions.

We have probed their electronic structure through

spectroscopy, electrochemistry, and Density Functional Theory (DFT) methods, and have elucidated the natures of the π-π* transitions using time-dependent DFT (TDDFT).


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NH

CR1R2

NH

+

H2CR1R2

HOAc

NH

NH

DII

CR1R2

1-4

O NC EtO

CN N H O

O

O

O O

OEt

O

O

O

O

O

N

N H

O O

3

O

O 2

1

O

O

N H

N

N

N H O

O

N

4

Scheme 1. Synthetic route for preparation of the compounds 1-4.


O


1

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2

3 Figure 1. The structures of compounds 1, 2, and 4 with 35% thermal ellipsoids. Non-ionizable hydrogen atoms have been omitted for clarity. Selected bond lengths and angles: C=C (Å): 1: 1.362(3), 1.366(3); 2: 1.382(2), 1.391(2); 3: 1.386(2), 1.397(2); C-Nisoindole (Å): 1: 1.371(3), 1.376(3); 2: 1.3649(19), 1.3722(19); 3: 1.3689(19), 1.372(2); N-O hydrogen bond heteroatom distance (Å): 1: 2.680 (2); 2.684 (2); 2: 2.598(2) 2.602(2); 3: 2.574(2), 2.546(2); C=C-Nisoindole angle (º): 1: 123.4(2), 123.6(2); 2: 120.00(13), 120.28(13); 3: 119.94(13), 120.63(13)


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Results and Discussion The formation of 1,3-diylideneisoindolene was first observed by Elvidge and Lindstead in 1956 upon the exposure of DII to an excess of ethylcyanoacetate.35 This chemistry was not extensively pursued in the chemical literature after this point, with the exception of some appearances in the dye patent literature.28-34 Recently, we rediscovered this chemistry with 5,5-dimethyl-1,3-cyclohexanedione (dimedone) as CHacid,36 and now found that we could extend it to a variety of organic CH-acids with activated methylene groups (pKa < 20). Additionally, the reaction can be optimized to use stoichiometric amounts of the organic acid by using glacial acetic acid as the solvent and the catalyst. The four compounds shown in Scheme 1 can be readily prepared in high yield and isolated as crystalline solids. The resultant materials, however can have limited solubility, which challenges characterization by spectroscopic methods such as 13C

NMR spectroscopy (compounds 3 and 4). However, all of the 1H NMR spectra for 1-4 exhibit the

expected resonances, with diagnostic AA’BB’ spin system patterns for the isoindoline aromatic protons as well as protons from the CH-acid fragments. We were able to elucidate the molecular structures of the ethylcyanoacetate (1), Meldrum’s (2), and dimethylbarbaturic (4) acid variants of the DYI compounds shown in Figure 1. The analogous barbaturic acid compound had been structurally elucidated previously.37 All three compounds characterized in this work are planar, with the exception of the sp3 hybridized carbons on the Meldrum’s acid derived species. In each case, the imine C=N double bonds of the parent DII has been replaced with alkene-type C=C bonds. The bond lengths for these alkene units are on the range of ~1.36-1.38 Å for the four compounds. Clearly these distances are slightly longer than a traditional carbon-carbon double bond, and inspection of the C-N bonds of the isoindoline unit (~1.36-1.37 Å) reveal some delocalization onto the ring. The central nitrogen in the isoindoline retains its ionizable hydrogen atom position, which engages in hydrogen bonding interactions with oxygen atoms from the organic acid groups.

The hydrogen bond length (as

measured from internal nitrogen atoms to oxygen atoms) range between 2.6 and 2.7 Å. Compounds 1-4



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exhibit a range of colors from red to yellow; the spectra of the four species are shown in Figure 2. All four compounds exhibit similar features in their spectra, with each showing three bands of increasing intensity with decreasing energy. It is tempting to correlate the UV-visible features of compounds 1-4, with the pKa of the component acid, but inspection of the values indicates that this trend does not exist. The pKa values for ethyl cyanoacetate, 1,3-indandione, Meldrum’s acid, and 5,5-dimethylbarbituric acid are 9.0, 8.9, 7.3, and 4.1 respectively, however the absorption maxima of the lowest energy bands for these compounds are 418, 489, 441, and 469 nm respectively. The extinction coefficients for these compounds are relatively large, on the order of ~2-9 x 104 M-1 cm-1. None of the four compounds exhibit any appreciable fluorescence.


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Figure 2. UV-visible spectra for compounds 1-4 in DCM.



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Figure 3. Cyclic voltammograms for compounds 1-4 recorded in DMF/0.1 TBAPF6 system at room temperature. Redox potentials (V) versus FcH/FcH+ are displayed in the table.


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The redox properties of all compounds were investigated using cyclic voltammetry (CV) approach (Figure 3). Each compound exhibits two quasi-reversible reduction processes. The first reduction potentials shift to more negative values in the order of 1 (most negative) < 3 ~ 4 < 2 (least negative). These values do not agree with the observed energies of transitions in the UV-visible spectra, which rank from 1 (highest energy) > 2 > 4 > 3 (lowest energy).

The gap between the first and a second reduction processes is

greatest for compound 1 (0.54 V), followed by 2, while compounds 3 and 4 show similar gaps (~0.41 V). We were not able to observe any oxidation processes in the electrochemical window. In order to understand the observed trends in UV-visible spectroscopy and electrochemistry, we further probed the electronic structures and optical spectroscopy of 1–4 using DFT and TDDFT calculations. The DFT-predicted frontier MOs and molecular energy diagram are presented in Figure 4. In all cases, the DFT-predicted HOMO and LUMO orbitals resemble each other. Indeed, the HOMOs of 1–4 are dominated by the contribution of the isoindole nitrogen atom, carbon atom directly attached to the isoindole fragment, and carbonyl oxygen atoms. The LUMOs for all compounds are dominated by the contributions from isoindole carbon atoms and C-C=O fragments directly attached to the isoindole terminal alkene units (Figure 4). It is interesting to note that the DFT-predicted differences in the energies of the LUMOs in 1-4 (E = 0.171 eV) are very small, but the energies of the HOMOs in these compounds varies more significantly (E = 0.360 eV).



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MO

Dye

LUMO+1

LUMO

HOMO

HOMO-1

1

3

3

4

Figure 4. DFT-predicted frontier orbitals (top) and energy levels (bottom) for compounds 1-4. ACS Paragon Plus Environment

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The experimental UV-vis spectra of compounds 1–4 correlate well with the TDDFT-predicted ones (Figure 5). In particular, the well-resolved experimental spectra of compounds 1 and 3 can be explained as follows. The low-energy, most intense band in these compounds is described as a predominantly HOMO → LUMO single-electron excitation predicted by TDDFT at 422 and 487 nm respectively. This band is complemented in experimental spectra by 0-1 and 0-2 vibronic satellites observed at 419 and 394 (compound 1) and 489 and 456 nm (compound 3), respectively. Such vibronic satellites are very characteristic for the previously reported isoindole functional dyes and their analogues. According to our TDDFT calculations, the higher-energy regions of the UV-vis spectra of 1 and 3 are dominated by the HOMO-n → LUMO single-electron transitions. In the case of dyes 2 and 4, in addition to the most intense HOMO → LUMO transitions, TDDFT predicts a large number of the HOMO-n → LUMO transitions in the visible energy envelope that are responsible for the broader experimental spectra of these compounds (Tables S6-9).



Figure 5. Experimental and TDDFT-predicted spectra for compounds 1-4.


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Conclusions In conclusion, we have revisited and expanded the chemistry of Linstead concerning the synthesis of a series of four 1,3-diylideneisoindolines. All of these compounds can be readily prepared in one-step from DII, and the four compounds are intensely colored. X-ray structural elucidation reveals planar structures, with the terminal alkene units clearly conjugated with the central isoindoline unit. These compounds exhibit intense absorption bands in the UV-and visible range, and the energies of these transitions are highly dependent on the structure of the organic acid substituent. DFT calculations reveal that these compounds exhibit similar LUMO energy levels, but that the HOMO energies vary depending on the alkene substituent and possess a significant degree of alkene character. We are continuing to explore the chemistry of the isoindolines as a means to produce new and novel chromophore systems. Experimental All reagents and starting materials were purchased from commercial vendors and used without further purification. 1,3-diiminoisoindoline (DII) was synthesized according to a previously published procedure.6 Deuterated solvents were purchased from Cambridge Isotope Laboratories and used as received. NMR spectra were recorded on a 300 MHz spectrometers and chemical shifts were given in ppm relative to residual solvent resonances (1H NMR and

13C

NMR spectra). High-resolution mass

spectrometry experiments were performed on a Bruker MicroTOF-III and MicroTOF-qIII instruments. Infrared spectra were collected on Thermo Scientific Nicolet iS5 that was equipped with an iD5 ATR. UV-visible spectra were recorded on a Hitachi 3010 and Jasco V-770 spectrometers. X-ray intensity data were measured on a Bruker CCD-based diffractometer with dual Cu/Mo ImuS microfocus optics (Cu Kα radiation, λ = 1.54178 Å, Mo Kα radiation, λ =0.71073 Å). Crystals were mounted on a cryoloop using Paratone oil and placed under a steam of nitrogen at 100 K (Oxford Cryosystems). The detector was placed at a distance of 5.00 cm from the crystal. The data were corrected



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for absorption with the SADABS program. The structures were refined using the Bruker SHELXTL Software Package (Version 6.1),38 and were solved using direct methods until the final anisotropic fullmatrix, least squares refinement of F2 converged. CCDC 1886266-1886268 contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures. Computational Details. The starting geometries of compounds 1-4 were optimized using a TPSSh exchange-correlation functional.39 Energy minima in optimized geometry was confirmed by the frequency calculations (absence of the imaginary frequencies). Solvent effect was modeled using the polarized continuum model (PCM).40 In all calculations, DCM was used as the solvent. In PCM-TDDFT calculation, the first 30 states were calculated. All atoms were modeled using 6-311G(d)41 basis set. Gaussian 09 software was used in all calculations.42 QMForge program was used for molecular orbital analysis.43 General synthetic procedure: A mixture of DII (1 mmol, 144 mg) and the corresponding CH- acid (2.1 eq) were dissolved in glacial acetic acid (10 mL) and refluxed for 1-3 min. Resulting solution was cooled down to room temperature, diluted with water, and filtered to give orange (or yellow) powder of pure compounds 1-4. Yields ranged from 71 – 90 %. Compound 1. 2,2'-(1H-isoindole-1,3(2H)-diylidene)-bis(cyanoacetic acid ethyl ester): Yield 254 mg (79 %). 1H NMR (300 MHz, CDCl3) δ: 13.08 (s, 1H), 8.68 – 8.65 (m, 2H), 7.82 – 7.79 (m, 2H), 4.44 (q, J = 7.1 Hz, 4H), 1.43 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz) δ: 168.7, 155.4, 133.6, 132.2, 126.0, 115.2, 80.0, 62.8, 14.2; IR (cm-1) 3278, 2994, 2979, 2222, 2213, 1699, 1683, 1592, 1469, 1453, 1368, 1272, 1221, 1169, 1156, 1141, 1093, 1018, 855, 768; HRMS (ESI-TOF, positive mode) m/z: calcd for C18H16N3O4 338.1110, found 338.1141 [M+H]+; UV-vis, nm ( x 104 M-1cm-1): 372 (2.03), 394 (3.71), 418 (3.98). Compound 2. 5,5'-(1H-isoindole-1,3(2H)-diylidene)bis-(2,2-dimethyl-1,3-dioxane-4,6-dione): Yield 283 mg (71 %). 1H NMR (300 MHz, CDCl3) δ 15.41 (s, 1H), 9.34 – 9.28 (m, 2H), 7.72 – 7.66 (m, 2H), ACS Paragon Plus Environment

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3.50 (s, 6H), 3.46 (s, 6H); 13C{1H} NMR (CDCl3, 125 MHz) δ: 164.3, 161.7, 159.7, 150.7, 134.5, 133.9, 131.2, 99.3, 29.2, 29.0; IR (cm-1) 3390, 2958, 2219, 2211, 1686, 1512, 1470, 1458, 1433, 1418, 1338, 1307, 1203, 1174, 1152, 1090, 773, 703, 703; HRMS (ESI-TOF, positive mode) m/z: calcd for C20H17NO8Na 422.0852, found 422.0842 [M+Na]+; UV-vis, nm ( x 104 M-1cm-1): 393 (1.91), 416 (2.65), 441 (2.88). Compound 3. 2,2'-(1H-isoindole-1,3(2H)-diylidene)bis-(1H-indene-1,3(2H)-dione): Yield 342 mg (85 %). 1H NMR (300 MHz, CDCl3) δ 14.30 (s, 1H), 9.73 – 9.70 (m, 2H), 8.05 – 8.00 (m, 4H), 7.87 – 7.82 (m, 6H); IR (cm-1) 3295, 3239, 1678, 1637, 1559, 1450, 1354, 1221, 1095, 1018, 881, 813, 730, 690, 658; HRMS (APCI-TOF, negative mode) m/z: calcd for C26H12NO4 402.0772, found 402.0785 [M-H]-; UV-vis, nm ( x 104 M-1cm-1): 370 (1.56), 387 (1.58), 425 (2.01), 458 (5.37), 489 (9.36). Compound

4.

5,5'-(1H-isoindole-1,3(2H)-diylidene)bis[1,3-dimethyl-2,4,6(1H,3H,5H)-pyrimidinetrione]:

Yield 380 mg (90 %) 1H NMR (300 MHz, CDCl3) δ 8.59 – 8.56 (m, 2H), 7.94 – 7.91 (m, 2H), 1.55 (s, 6H); IR (cm-1) 3015, 1965, 1716, 1662, 1633, 1581, 1512, 1461, 1438, 1414, 1387, 1373, 1328, 1314, 1292, 1259, 1217, 1193, 1169, 1105, 1065, 1053, 1042, 974, 945, 871, 818, 799, 788, 765, 756, 750, 717, 687, 682, 671, 619; HRMS (ESI-TOF, positive mode) m/z: calcd for C20H17N5O6Na 446.1070, found 446.1077 [M+Na]+; UV-vis, nm ( x 104 M-1cm-1): 421 (1.77), 447 (3.12), 474 (3.90).

ASSOCIATED CONTENT Supporting Information Characterization data for compounds 1 – 4, including cyclic voltammograms, CIF files and X-ray crystallographic data as well as Cartesian coordinate and TDDFT data for all optimized structures.

AUTHOR INFORMATION Corresponding Authors E-mail: [email protected] ACS Paragon Plus Environment


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E-mail: [email protected] ORCID Victor Nemykin: 0000-0003-4345-0848 Christopher J. Ziegler 0000-0002-0142-5161 Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS Generous support from the Minnesota Supercomputing Institute, NSERC, University of Manitoba, and WestGrid Canada to VN is greatly appreciated.

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TOC figure



CR1R2

NH NH

Page 22 of 22

+

HOAc

2 eq. H2CR1R2

NH

NH

1-4

CR1R2 O

O

O H2CR1R2 =

NC

C H2 1

OEt

O

N

O C H2 2

O

O

C H2

O

O

3


N C H2 4

O

1,3-Diylideneisoindolines: Synthesis, Structure, Redox, and Optical

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