Synthesis, Optical Characterization in Solution and Solid-State, and DFT Calculations of 3-Acetyl and 3-(1′-(2′-Phenylhydrazono)ethyl)-coumarin-(7)-substituted Derivatives

Abstract

Intramolecular charge transfer (ICT) effects are responsible for the photoluminescent properties of coumarins. Hence, optical properties with different applications can be obtained by ICT modulation. Herein, four 3-acetyl-2H-chromen-2-ones (1a–d) and their corresponding fluorescent hybrids 3- (phenylhydrazone)-chromen-2-ones (2a–d) were synthesized in 74–65% yields. The UV-Vis data were in the 295–428 nm range. The emission depends on the substituent in position C-7 bearing electron-donating groups. Compounds 1b–d showed good optical properties due to the D-π-A structural arrangement. In compounds 2a–d, there is a quenching effect of fluorescence in solution. However, in the solid, an increase is shown due to an aggregation-induced emission (AIE) effect given by the rotational restraints and stacking in the crystal. Computational calculations of the HOMO-LUMO orbitals indicate high absorbance and emission values of the molecules, and gap values represent the bathochromic effect and the electronic efficiency of the compounds. Compounds 1a–d and 2a–d are good candidates for optical applications, such as OLEDs, organic solar cells, or fluorescence markers.

1. Introduction

Intramolecular charge transfer (ICT), as well as linear and nonlinear optical properties [1,2,3,4,5], are associated with organic molecules having an extended electronic π-backbone. This molecular characteristic is generally modulated by the insertion of electron-donor or -acceptor groups into the electronic π-system, to favor the ICT [6]. The typical electronic architectures that can be presented, are donor-acceptor-donor (D-A-D), donor-π-acceptor (D-π-A), or donor-π-acceptor-π-donor (D-π-A-π-D), known as push-pull type compounds. Photoluminescent compounds and materials with fluorescent and phosphorescent properties play a fundamental role in many areas, such as biology, pharmacology, chemistry, biomedicine, and optoelectronics [7,8,9,10,11,12]. For example, coumarin compounds coupled to phenylhydrazine have been reported as fluorescent probes for visualizing living tissues [13]. Photoluminescent organic compounds derived from coumarins have been applied in two-photon absorption phenomena, optical data storage, energy limitation, and the manufacture of lasers [5]. Coumarins can be obtained in good yields [9] through synthetic techniques, such as Knoevenagel, Pechmann, and Wittig reactions. Therefore, the photophysical properties of coumarins can be easily modified by substituting in positions 3, 6, 7, and 8 to obtain hybrid materials [9,14,15], which exhibit high quantum yields, important changes in Stokes shifts, and good absorption and emission profiles [16]. On the other hand, fluorescent hybrid compounds derived from hydrazines and coumarins have shown synergic effects in their fluorescent properties [17,18]. These compounds have been applied as on-off sensors [19,20], photoluminescent dyes [21], anticonvulsants [22], hydrogels [23], and antimicrobials [24].

In this work, we describe the synthesis, structural characterization, and photoluminescence proprieties of small compounds derived from 3-acetyl-2H-chromene-2-one (1a–d) coupled with phenylhydrazine, forming the hybrid fluorescent compounds 3-(1′-(2′-phenylhydrazono) ethyl)-2H-2-chromen-2-one (2a–d). The optical characterization of 2a–d was performed in solution and in the solid-state, and the results contrasted with ab initio theoretical calculations. The UV-vis spectra of coumarins 1a,c and 2b have been reported in solution but not in the solid-state [25,26].

2. Experimental

2.1. Materials and Methods

Salicilaldehyde, 4-methoxy-salicylaldehyde, 4-hydroxy-salicylaldehyde, 4-diethylamino-salicylaldehyde, ethyl acetoacetate, piperidine, glacial acetic acid, ethanol, and phenylhydrazine were purchased from Aldrich (Toluca, Mexico) and used as received. The ACS grade solvents were purchased from CTR (Jalisco, Mexico) and used without further purification. Melting points were measured on an Electrothermal Mel-Temp 1201D apparatus. IR spectra were collected using Varian 3100 FT-IR EXCALIBUR series spectrophotometer. ¹H and ¹³C NMR spectra were recorded in a BRUKER Ultrashield plus 400 MHz in DMSO-d₆ solutions using (CH₃)₄Si as an internal reference compound; chemical shifts (δ) are in ppm and coupling constants (ⁿJ_H-H) in Hz. Mass analysis was performed by electro spray ionization in a high-resolution mass spectrometer Bruker micOTQF- QTOF instrument (Bruker Daltonik GmbH, Bremen, Germany). Absorbances were obtained with a Perkin Elmer Lambda 900 UV/Vis/IR spectrophotometer; emissions were obtained in an Edinburan F55 fluorometer, employing the stock solutions of 1 × 10⁻³ M of compounds 1a–d and 2a–d. The fluorescence spectra were recorded under 400 nm excitation (except in the compound 2d was in 372 nm). The quantum efficiencies were obtained using an integration sphere of direct photon counting, relating the absorbed and emitted photons. The optical data in the solid state were obtained similarly.

2.2. General Methods of Synthesis and Characterization

3-Acetyl-2H-chromene-2-one (1a–d) were prepared following reported procedures [15,27] with modifications. 4-Substituted-salicylaldehydes, ethyl acetoacetate, and piperidine were dissolved in 15 mL of ethanol and placed under reflux at 78 °C for 24 h. After cooling, the solvent was removed by vacuum filtration, and the resulting solid was recrystallized from cold ethanol.

3-Acetyl-2-chromen-2-one (1a) [25]. Obtained from salicilaldehyde (0.42 mL, 4.1 mmol), ethyl acetoacetate (0.51 mL, 4.1 mmol), and piperidine (17.4 μL, 3 drops). White solid, yield = 0.62 g (80%), mp = 94–96 °C. λ Abs (nm) = 297 (THF), 296 (acetonitrile). IR (cm⁻¹): ν (C-H) 2978, ν (C-H aromatic) 3047, ν (C=C) 1674–1450, ν (C=O) 1681, ρ (C-H f.p) 771. ¹H-NMR (DMSO-d6), δ (ppm): 8.67 (1H, s, H-4), 7.95 (1H, d, ³J 8.3, H-5), 7.74 (1H, dd, ³J 7.7, 7.3, H-7), 7.48 (1H, d, ³J 7.7, H-8), 7.44 (1H, d, ³J 8.3, 7.3, H-6), 2.51 (3H, s, H-12). ¹³C-NMR (DMSO-d₆), δ (ppm): 195.5 (C-11), 158.8 (C-2), 155.0 (C-9), 147.4 (C-4), 134.9 (C-7), 131.2 (C-5), 125.4 (C-6), 124.9 (C-3), 118.6 (C-10), 116.5 (C-8), 30.4 (C-12).

3-Acetyl-7-diethylamino-2-chromen-2-one (1b) [28,29]. Obtained from 4-diethylamino-salicylaldehyde (0.500 g, 2.6 mmol), ethyl acetoacetate (0.32 mL, 2.6 mmol) and piperidine (17.4 μL, 3 drops). Yellow solid, yield = 0.37 g (59%), mp = 156–158 °C. λ Abs (nm) = 426 (THF), 429 (acetonitrile), 424 (toluene), λ Em (nm) = 466 (THF), 477 (acetonitrile), 461 (toluene). IR (cm⁻¹): ν (C-H) 2924, ν (C-H aromatic) 2962, ν (C=C) 1608–1411, ν (C=O) 1658, ν (C-N) 1188, ρ (C-H f.p) 759. ¹H-NMR (DMSO-d6), δ (ppm): 8.4 (1H, s, H-4), 7.65 (1H, d, ³J 9.0, H-5), 6.78 (1H, dd, ³J 9.0, ⁴J 2.4, H6), 6.56 (1H, d, ⁴J 2.3, H-8), 3.9 (3H, s, H-12), 3.49 (4H, q, ³J 7.0, N (CH₂CH₃)₂.), 1.14 (6H, t, ³J 7.0, N (CH₂CH₃)₂.). ¹³C-NMR (DMSO-d6), δ (ppm): 194.6 (C-11), 160.3 (C-2), 158.7 (C-9), 153.4 (C-7), 148.0 (C-4), 132.8 (C-5), 115.5 (C-3), 110.6 (C-6), 107.9 (C-10), 96.3 (C-8), 44.8 (N (CH₂CH₃)₂.), 12.8 N (CH₂CH₃)₂.

3-Acetyl-7-hydroxy-2-chromen-2-one (1c) [30]. Obtained from 4-hydroxy-salicylaldehyde (0.500 g, 3.62 mmol), ethyl acetoacetate (0.42 mL, 3.6 mmol) and piperidine (17.4 μL, 3 drops). Green solid, yield = 0.68 g (89%), mp = 240–242 °C. λ Abs (nm) = 359 (THF), 356 (acetonitrile), λ Em (nm) = 460 (THF), 453 (acetonitrile). IR (cm⁻¹): ν (C-H) 2927; ν (C-H aromatic) 3032, ν (C=C) 1678–1450, ν (C=O) 1678; ν (O-H) 3194, ρ (C-H f.p) 763. ¹H-NMR (DMSO-d6), δ (ppm): 8.57 (1H, s, H-4), 7.65 (1H, d, ³J 8.6, H-5), 6.86 (1H, dd, ³J 8.6, ⁴J 2.2, H-6), 6.73 (1H, d, ⁴J 2.2, H-8), 2.63 (3H, s, H-12). ¹³C-NMR (DMSO-d6), δ (ppm): 195.1 (C-11), 165.1 (C-2), 159.5 (C-9), 157.8 (C-7), 148.2 (C-4), 133.1 (C-5), 119.4 (C-3), 114.8 (C-6), 111.1 (C-10), 102.2 (C-8), 30.4 (C-12).

3-Acetyl-7-methoxy -2-chromen-2-one (1d) [31]. Obtained from 4-methoxy-salicylaldehyde (0.500 g, 3.28 mmol), ethyl acetoacetate (0.41 mL, 3.3 mmol) and piperidine (17.4 μL, 3 drops). Yellow solid, yield = 0.63 g (87%), mp = 172–174 °C. λ Abs (nm) = 356 (THF), 354 (acetonitrile). IR (cm⁻¹): ν (C-H) 2978, ν (C-H aromatic) 3032, ν (C=C) 1666–1462, ν (C=O) 1670, ν (C-O-C) 1126, ρ (C-H f.p) 767. ¹H-NMR (DMSO-d6), δ (ppm): 8.62 (1H, s, H-4); 7.86 (1H, d, ³J 8.6, H-5), 7.02 (1H, dd, ³J 8.6, H-6), 7.04 (1H, s, H-8), 2.56 (3H, s, H-12), 3.9 (3H, s, OMe). ¹³C-NMR (DMSO-d6), δ (ppm): 195.1 (C-11), 165.3 (C-2), 159.3 (C-9), 157.5 (C-7), 148.0 (C-4), 132.6 (C-5), 120.8 (C-3), 113.9 (C-6), 112.2 (C-10), 100.7 (C-8), 56.7 (OMe), 30.4 (C-12).

Compounds 2a,c were prepared according to previous reports [31]. Compounds 2b,d have not been reported yet. The corresponding 4-substituted compound 1a–d, phenylhydrazine, and glacial acetic acid were added to 10 mL of ethanol and refluxed at 78 °C for 4 h. The solvent was removed by gravity filtration, and the solid was washed with ethanol, recrystallized from ethanol at room temperature, and then characterized.

3-(1-(2-Phenylhydrazone) ethyl) 2-chromen-2-one (2a) [32]. Obtained from 1a (0.300 g, 1.07 mmol), phenylhydrazine (0.105 mL, 1.07 mmol) and glacial acetic acid (13.6 μL, 3 drops). Orange solid, yield = 0.39 g (74%), mp = 184–186 °C. λ Abs (nm) = 277 (THF), 275 (acetonitrile). IR (cm⁻¹): ν (C-H) 2978, ν (C-H aromatic) 3032, ν (C=C) 1597–1489, ν (NH) 3294, ν C=N (1597), ρ (C-H f.p) 732. ¹H-NMR (DMSO-d6), δ (ppm): 9.46 (NH, s), 8.20 (1H, s, H-4), 7.84 (1H, d, ³J 7.8, H-5), 7.60) (1H, dd, ³J 7.9, 7.4, H-7), 7.41 (1H, d, ³J 8.0, H-8), 7.36 (1H, dd, ³J 7.9, 7.5, H-6), 7.21–7.27 (4H, o, m, -Ph), 6.79 (1H, p, ³J 7.0, -Ph). 2.23 (3H, s, H-12), ¹³C-NMR (DMSO-d6), δ (ppm): 160.4 (C-2), 153.4 (C-9), 146.0 (C-11), 139.6 (C-4), 139.1 (ipso, -Ph), 132.0 (C-7), 129.3 (C-5), 129.2 (m, -Ph), 127.8 (C-3), 125.0 (C-6), 119.8 (C-10), 119.7 (p, -Ph), 116.3 (C-8), 113.5 (o, -Ph), 15.5 (C-12).

7-(Diethylamino)-3-(1-(2-phenylhydrazone)ethyl)2-chromen-2-one (2b). Obtained from 1b (0.300 g, 1.15 mmol), phenylhydrazine (0.113 mL, 1.15 mmol) and glacial acetic acid (13.6 μL, 3 drops). Orange solid, yield = 0.32 g (65%), mp = 236–238 °C. λ Abs (nm)= 411 (THF), 413 (acetonitrile), 408 (toluene), λ Em (nm) = 479 (THF), 494 (acetonitrile), 469 (toluene). IR (cm⁻¹): ν (C-H) 2900; ν (C-H aromatic) 2966; ν (C=C) 1589–1408, ν (NH) 3302, ν C=N (1589), ρ (C-H f.p) 748. ¹H-NMR (DMSO-d6), δ (ppm): 9.23 (NH, s), 8.01 (1H, s, H-4), 7.56 (1H, d, ³J 8.9, H-5), 7.22-7-20 (4H, o, m, -Ph), 6.73 (1H, p, -Ph), 6.71 (1H, d, ³J 8.9, H-6), 6.55 (1H, s, H-8), 2.20 (3H, s, H-12), 3.45 (4H, q, ³J 6.9, (N (CH₂CH₃)₂), 1.14 (6H, t, ³J 7.0, N (CH₂CH₃)₂), ¹³C-NMR (DMSO-d6), δ (ppm): 160.9 (C-2), 156.4 (C-9), 150.9 (C-7), 146.4 (C-11), 140.4 (ipso, -Ph), 140.6 (C-4), 130.2 (C-5), 129.2 (m, -Ph), 120.1 (C-3), 119.3 (p, -Ph), 113.4 (m, -Ph), 109.7 (C-6), 108.6 (C-10), 96.6 (C-8), 44.5 (N (CH₂CH₃)₂), 15.7 (C-12), 12.8 (N (CH₂CH₃)₂). MS-MS (ESI) m/z = 350.1866 [M + H]⁺ (experimental), 350.1869 (calculated).

7-(Hydroxy)-3-(1-(2-phenylhydrazone)ethyl)-2-chromen-2-one (2c) [26]. Obtained from 1c (0.300 g, 1.46 mmol), phenylhydrazine (0.144 mL, 1.46 mmol) and glacial acetic acid (13.6 μL, 3 drops). Yellow solid, yield = 0.36 g (65%), mp = 228–230 °C. λ Abs (nm) = 278 (THF), 276 (acetonitrile), λ Em (nm) = 465 (THF). IR (cm⁻¹): ν (C-H aromatic) 3032; ν (C=C) 1593–1442, ν (NH) 3325, ν (O-H) 3221 ν (C=N) 1597, ρ (C-H f.p) 748. ¹H-NMR (DMSO-d6), δ (ppm): 10.62 (1H, s, OH) 9.31 (NH, s), 8.09 (1H, s, H-4), 7.66 (1H, d, ³J 8.4, H-5), 6.81 (1H, d, ³J 8.4, H-6), 6.74 (1H, s, H-8), 7.22 (4H, o, p, -Ph), 6.77 (1H, p, -Ph), 2.20 (3H, s, H-12). ¹³C-NMR (DMSO-d6), δ (ppm): 161.6 (C-7), 160.4 (C-2), 155.5 (C-9), 146.0 (C-11), 140.4 (C-4), 139.7 (ipso, -Ph), 130.6 (C-5), 129.2 (m, -Ph), 123.3 (C-3), 119.6 (p, -Ph), 113.9 (C-6), 113.4 (o, -Ph), 112.2 (C-10), 102.2 (C-8), 15.6 (C-12).

7-(Methoxy)-3-(1-(2-phenylhydrazone)ethyl)-2-chromen-2-one (2d). Obtained from 1d (0.300 g, 1.48 mmol), phenylhydrazine (0.148 mL, 1.46 mmol) and glacial acetic acid (13.6 μL, 3 drops). Yellow solid, yield = 0.41 g (65%), mp = 228–230 °C. λ Abs (nm) = 278 (THF), 275 (acetonitrile), λ Em (nm) = 467 (THF). IR (cm⁻¹): ν (C-H) 2997, ν (C-H aromatic) 3020, ν (C=C) 1612–1496, ν (NH) 3309, ν (C=N) 1608, ρ (C-H f.p) 736. ¹H-NMR (DMSO-d6), δ (ppm): 9.36 (NH, s), 8.15 (1H, s, H-4), 7.77 (1H, d, ³J 8.65 H-5), 7.23–7.22 (4H, o, m, -Ph); 7.0 (1H, s, H-8), 6.98 (1H, d, ³J 8.6, H-6), 6.79 (1H, p, -Ph), 3.88 (3H, s, OMe), 2.21 (3H, s, H-12), ¹³C-NMR (DMSO-d6), δ (ppm): 162.8 (C-2), 160.3 (C-2), 155.4 (C-9), 146.1 (C-11), 140.1 (C-4), 139.5 (ipso, -Ph), 130.3 (C-5), 129.3 (m, -Ph), 124.3 (C-3), 119.6 (p,-Ph), 113.5 (C-6), 113.3 (o, -Ph), 113.3 (C-6), 100.7 (C-8), 56.4 (OMe), 15.5 (C-12). MS-MS (ESI) m/z = 309.1235 [M + H]⁺ (experimental), 309.1239 (calculated).

2.3. Determination of Quantum Yield

Fluorescence quantum yield (Φ) for coumarins (1a–d) and hydrazones (2a–d) were measured through the integration sphere direct excitation method, with “Direct Excitation” measurements, which record the scatter and the emission of the sample being directly excited by the radiation from the excitation monochromator only. The absolute fluorescence quantum yield (Φ) is the ratio of the number of photons emitted to the number of photons absorbed, according to Equation (1).

$$\varphi =\frac{N^{em}}{N^{abs}}$$ (1)

The absolute fluorescence quantum yield (Φ_Dexc) was calculated with the direct excitation method according to Equation (2).

$${\varphi }_{Dexc}=\frac{E_B-E_A}{S_A-S_B}$$ (2)

where E denotes the emission region of sample and solvent, S the excitation scatter region of sample and solvent, and A, B the experimental setup and integral of the scans of samples and solvent.

For calculating the integrals, the selection of the integral regions, and the final calculation of Φ_Dexc, we used the quantum yield wizard supplied with the equipment software [33].

2.4. Computational Details

Geometry optimizations were carried out using the framework of density functional theory implemented in ORCA software [34]. For the exchange and correlation, the PBE0 hybrid functional [35,36] was combined with a complete electronic basis set aug-cc-pVDZ [37]. A vibrational frequency analysis was effectuated to verify minima energy states; only positive values were found in all cases. The HOMO-LUMO gap energies were calculated, and frontier orbitals were plotted using Chemcraft [38]. Excited states were determined using TD-DFT [39,40,41] under the same level of theory PBE0/aug-cc-pVDZ [42], and solvent effects were included using a conductor-like polarizable model (CPCM) [43,44] considering THF, acetonitrile, and toluene.

3. Results and Discussion

3.1. Synthesis and Structural Characterization

Coumarins 1a–d were synthesized by the Knoevenagel [28] condensation of ethyl acetoacetate with the corresponding 4-substituted salicylaldehyde (Scheme 1), with yields higher than 80%. Afterward, the functionalization of 3-acetyl-coumarin derivatives 1a–d with phenylhydrazine was performed through acid catalysis with glacial acetic acid to obtain compounds 2a–d (Scheme 1). The experimental yields are in the 65–74% range, according to precise reports about the synthesis of the same compounds [2,29,32,45].

Scheme 1.

Synthesis of 3-acetyl-2H-chromen-2-one (1a–d) and 3-(1-(2-phenylhydrazone)ethyl)-2-chromen-2-one (2a–d).

The H-4 signal in the ¹H NMR spectra indicated the formation of compounds 1a–d (Figures S1–S8), appearing in the 8.40–8.67 ppm range [31]. The functionalization with phenylhydrazine in compounds 2a–d, generated an anisotropic effect perpendicularly extended from the phenyl group of the hydrazone fragment to the pyran ring, causing the protection of H-4 and shifting the signal to lower frequencies in the 8.00–8.15 ppm range. The NH proton in the phenylhydrazone was shifted to high frequencies appearing in the 9.31–9.46 ppm range; whereas the ¹³C-NMR signal was shielded from 194.6–195.5 ppm, for compounds 1a–d, to the range of 146.0–146.4 ppm in compounds 2a–d (Figures S9–S16). The IR spectra of compounds 1a–d showed the C=O band in the 1658–1681 cm⁻¹ range. Meanwhile, compounds 2a–d showed the characteristic hydrazone C=N and N-H bands in the 1589–1608 cm⁻¹ and 3294–3325 cm⁻¹ ranges, respectively. Selected ¹H and ¹³C NMR values and IR wavenumbers are listed in Table 1.

Table 1.

Selected ¹H, ¹³C NMR (δ = ppm, DMSO-d6) and IR (ν = cm⁻¹) spectroscopic data for compounds 1a–d and 2a–d.

Comp.	δ 1H	δ 13C	ν/cm−1	Comp.	δ 1H		δ 13C	ν/cm−1	ν/cm−1
	H-4	C-11	C=O		H-4	N-H	C=N	N-H	C=N
1a	8.67	195.5	1681	2a	8.00	9.46	146.0	3294	1597
1b	8.40	194.6	1658	2b	8.01	9.23	146.4	3302	1589
1c	8.57	195.1	1678	2c	8.09	9.31	146.0	3325	1597
1d	8.62	195.1	1670	2d	8.15	9.36	146.1	3309	1608

3.2. UV-vis Absorption and Photoluminescence Spectra

The UV-vis and fluorescence spectroscopic data of compounds 1a–d and 2a–d, measured in tetrahydrofuran and acetonitrile solvents at room temperature, are listed in Table 2. Their scarce solubility in solvents, such as ethanol, DMF, and water, limited the tests in these solvents. The absorption and emission spectra in solution are shown in Figure 1 and Figure 2, respectively. The maximum absorbance bands are attributed to π → π* and n → π* electronic transitions. The absorption band in 1b–d showed a red-shift due to the insertion of electron-donor substituents in the C-7 position. The largest red-shift in 1b is attributed to the strong electron-donor character of the diethylamino group [4,9]. Similar behavior is conserved in phenylhydrazone derivatives, wherein 2b shows the largest bathochromic effect in the absorption band. The molar absorptivity depends on the solvent used, obtaining higher values with acetonitrile than with THF. In contrast to the full palette observed in the absorption, compounds 1a,d and 2a showed no emission band. The maximum wavelength of the coumarin emission band is around 453–494 nm. The increase of emission is related to the nature of the substituent in C-7 following the order: N (CH₂CH₃)₂ > OH > OCH₃ > H, in agreement with the strength of the substituent electron-donor properties [4,9]. Compound 1b showed the largest quantum yield (Φ_F) with values above 80%.

Table 2.

Experimental photophysical properties in a solution of compounds 1a–d and 2a–d.

Compound	Solvent	λmaxAbs	ε (M−1 cm−1)	λmax Em	Stokes Shift (cm−1)	ΦF (%)
1a	THF Acetonitrile	297 296	100,870 138,563	NO NO	NO NO	NO NO
1b	THF Acetonitrile	426 429	42,277 45,357	466 477	2014 2345	6 80
1c	THF Acetonitrile	359 356	194,444 196,477	460 453	6116 6014	>1 >1
1d	THF Acetonitrile	356 354	238,403 244,724	NO NO	NO NO	NO NO
2a	THF Acetonitrile	277 275	21,480 268,504	NO NO	NO NO	NO NO
2b	THF Acetonitrile	411 413	31,247 39,880	479 494	3454 3970	>1 2
2c	THF Acetonitrile	278 276	16,525 235,090	465 NO	14465 NO	>1 NO
2d	THF Acetonitrile	278 275	17,588 237,623	467 NO	14557 NO	>1 NO

THF = Tetrahydrofuran, Quantum Yield (Φ_F). λ^ex(Em) = λ_max(Abs). NO Not Observed.

Figure 1.

Absorption UV-vis spectra of compounds 1a–d and 2a–d (c = 1 × 10⁻⁴ M, at 25 °C) in (a) THF, and (b) acetonitrile.

Figure 2.

Fluorescence spectra of compounds 1b,c, 2b–d in THF and 1b,c, 2b in acetonitrile solutions (c = 1 × 10⁻⁴ M, at 25 °C). λ^ex (Em) = λ_max (Abs). Compound 2c,d do not have emission.

On the other hand, a brief comparison between the photophysical properties of coumarins 1a–d with the corresponding values of hydrazones 2a–d allowed us to conclude that coumarin functionalization in the C-3 position with hydrazine caused fluorescence quenching with null fluorescence yields. This result is explained by the diminished electron acceptor capabilities of the resulting hydrazone functionality.

Compounds 1b,d, and 2c showed the best photophysical properties in the solid-state. Their fluorescence spectra are shown in Figure 3, and their photophysical properties are listed in Table 3. The emission λ_max of coumarin 1b was red-shifted to 595 nm in comparison with the solution (477 nm), and unexpectedly, compound 1d turned emissive, showing a band at 540 nm, although with low Φ_F values (<6.6%) in both cases. In contrast, hydrazone 2c has emissive properties compared to the solution: emission at 582 nm and Φ_F value of 52.6. These results revealed that the intermolecular interactions in the solid-state favor the emissive relaxation mechanism from an excited state. The X-ray molecular structures of compounds 1a,b,d are known [46,47,48,49]. Hence, a brief analysis of their photoluminescent properties in relation with their molecular structure in the solid state seems appropriate. The powder X-ray diffractogram of 1a,b,d was obtained and compared to the single crystal reported ones, shown in Figure S17. In the solid, the free rotation of the pendant –OMe and 3-Ac groups is restricted due to intermolecular hydrogen bonds, leading to a coplanar system and increasing the emissive properties of 1d. Therefore, the solid-state exerts an aggregation-induced emission (AIE) effect [46] on 1d. In the solid, the molecules of 1d are π-stacked along the (100) direction, at a distance of 3.509 Å between the benzo fused (Bz) and lactone (L) rings centroids (Cg (Bz)-Cg (L)) [47], in agreement with medium strength π-D-π-A interactions arranged in the head-to-tail fashion [50]. It is worth mentioning that the Bz ring acts as the donor and the L ring as the acceptor. In contrast, coumarin 1a crystallizes in two forms, triclinic (form A) and monoclinic (form B). Form A (herein obtained) is a head-to-head stacked, while form B generates head-to-tail π-stacked dimers with long Cg (Bz)-Cg (L) distances of 4.77 Å and 3.98 Å, respectively [48]. On the contrary, an aggregation-caused quenching (ACQ) effect is observed on 1b. In the crystal lattice, the molecules of 1b are arranged in dimers through antiparallel type carbonyl–carbonyl interactions [51] at Cg (Bz)-Cg (L) distance of 6.38 Å and the amino-ethyl groups pointing to opposite directions [49]. The free rotation of the pendant –NEt₂ and 3-Ac groups in 1b is restricted as in 1d, but with the contrary effect. This brief analysis supports that the Φ_F in the solid-state depends on the crystal lattice arrangement. Coumarin molecules that show head-to-tail π-staking arrangement with a Cg(Bz)-Cg(L) distance shorter than 3.5 Å seem to favor large Φ_F values. The large value of Φ_F of hydrazone 2c in the solid-state is also explained as an AIE effect. Intermolecular hydrogen bonding, probably between the –OH and the C=N functionality, should favor an entire head-to-tail π-staking arrangement in the crystal lattice with the appropriate Cg (Bz)-Cg (L) distance, as mentioned earlier.

Figure 3.

Fluorescence spectra in the solid-state of compounds 1b,d, and 2c (at 25 °C).

Table 3.

Photophysical properties of compounds 1b,d, and 2c in the solid-state.

Compound	λmax Em (nm)	ΦF (%)
1b	595	<1
1d	540	6.6
2c	582	52.6

Compounds 1–5 have been used as fluorescent dyes for cellular imaging (1), indicators of bathochromic effects with red emissions (2), chemosensors for anions (3), for the study of nonlinear optical properties (4), and observation of highly fluorescent compounds depending on the substituents (5). Their photophysical properties are listed in Table 4. 7-Diethylamino substituted coumarin 1b showed better photophysical properties (Φ_F) in solution than compounds 1–5, previously reported and shown in Figure 4 [6,7,10,16,52]. Then, compound 1b in solution and 2c in the solid-state could be evaluated in similar applications, since they have even better optical properties, and their synthesis is simpler and with higher chemical yields than the reported compounds 1–7.

Table 4.

Reported photophysical properties of 7-diethylamino-coumarins, used for comparison purposes.

Structure	Absorbance (nm)	Emission (nm)	ΦF (%)	References
1	379	501 (479)	71 (42)	[7]
2	510	585	>1	[16]
3	406	482	>1	[52]
4	432	490	NR	[6]
5	436	544	>1	[10]
6	316	458	NR	[53]
7	527	551	NR	[54]

NR = Not reported; (Emission in solid-state).

Figure 4.

Reported coumarin compounds with photophysical properties in solution, used for comparison purposes [6,7,10,16,52,53,54].

3.3. Theoretical Calculations

The theoretical data of the molecular orbitals allowed us to explain the spectroscopic behavior and the electronic effects in the molecules. The HOMO (H), LUMO (L), H-L gap, and Eg^op energy values are listed in Table 5. The H-L gap energies are similar among them. Nevertheless, the smallest value corresponds to compound 1b, whose λ_max is displaced towards the red. Likewise, the H-L gap represents the excited state electronic transition [6,38] from S₀ to S₁. Compounds 2a–d show low H-L gap values similar to coumarins 1a–d. The theoretical values, listed in Table 5, agree with the experimental optical values.

Table 5.

HOMO-LUMO (H-L) gap values of compounds 1a–d and 2a–d. Data are calculated at aug-cc-pVDZ/PBE0 level of theory. Experimental Eg^op values are also shown.

Compound	HOMO (eV)	LUMO (eV)	H-L Gap (eV)	Egop (eV) *
1a	−7.28	−2.80	4.47	4.18
1b	−6.29	−2.44	3.84	2.90
1c	−6.93	−2.60	4.32	3.50
1d	−6.81	−2.53	4.28	3.56
2a	−5.34	−2.51	2.83	4.52
2b	−4.93	−2.05	2.88	3.03
2c	−5.57	−2.57	3.00	3.28
2d	−5.18	−2.29	2.88	3.34

* Obtained from equation Eg^op = 1243/λ (values obtained from highest wavelengths in Table 2).

The optical gap values (Eg^op) for coumarins rank from 2.90 to 4.18 eV, and they are smaller than the theoretical data (3.84–4.47 eV); where compound 1b shows the smallest Eg^op value, indicating good ICT capability. Eg^op values of compounds 2a–d show low energy values (3.03–4.52 eV) like coumarins. These results indicate that the absorbance and emission red-shifts are due to the good electronic efficiency in their D-A structure. The theoretical and experimental H-L gap values are in agreement with the experimental optical properties and increase their possibility to function as semiconductor compounds [55]. The experimental values are comparable with the data for well-known luminophores 3, 6, and 7 listed in Table 6 and whose structures are shown in Figure 5.

Table 6.

Comparison of reported theoretical calculations with compounds 1a–d y 2a–d.

Compounds	HOMO (eV)	LUMO (eV)	Gap (eV)	References
3	−5.68 to −1.83	−2.15 to 0.38	NR	[52]
6	−6.21 to −6.35	−2.39 to −2.51	3.69 to 3.95	[53]
7	−5.17 to −5.34	−2.10 to −3.19	1.98 to 2.47	[54]

NR = Not reported.

Figure 5.

Frontier molecular orbitals corresponding to the optimized structures of compounds 1a–d.

The data of compounds 1b–d showed HOMO-LUMO interactions (Table S1) in a higher percentage of contribution energy due to the ED groups generating n → π* transitions, in contrast to compound 1a, which causes HOMO-1-LUMO π → π* transitions, in agreement with the experimental data.

Compounds 2a–d showed π → π* and n → π*transitions represented by the HOMO-LUMO, HOMO+1-LUMO-1 orbitals (supplementary material Table S2), indicating a D-A behavior of the molecules which is consistent with the experimental data.

Figure 5 shows the FMOs (frontier molecular orbitals) of compounds 1a–d. The structures show a planar geometry through the benzopyran ring. The HOMO-LUMO and HOMO-1-LUMO electronic distributions indicate the presence of π → π* and n → π* transitions, confirming the excitation of the FMOs from S₀ to S₁.

In compounds 2a–d, the phenylhydrazine group acts as an ED group. In this case, it represents the energy of the HOMO, and often, the whole part of the coumarin where the substituent in the benzopyrone ring acts as EA group, represented by the energy of the LUMO (Figure 6). The previous result agrees with the experimental findings, suggesting that the electronic cloud of the ED moiety moves towards the EA, which is from the phenylhydrazine to the coumarin. The hydrazo-coumarins 2a–d showed low quantum yields and unobservable emissions because the electronic cloud does not include the ED group which is interacting with the solvents.

Figure 6.

Frontier molecular orbitals corresponding to the optimized structures of compounds 2a–d.

Compound 2c shows different behavior in the FMOs, and its electron density is both as HOMO and LUMO in the hydrazone group, generating only n → π* type transitions, which agrees with its behavior in the solid-state, since the solvent generates the quenching of the fluorescence in solution.

4. Conclusions

Molecules 1a–d and 2a–d can be good candidates for semiconductor compounds suitable to be used in several optical applications. The photophysical properties of coumarins 1a–d and their hydrazone derivatives 2a–d were compared. The bandgap indicates the efficient ICT, which confirms the D-A type structure. Compounds 1b and 2c presented the best optical properties. Compound 1b showed absorbances at λ > 420 nm and emission at λ > 460 nm in solution and quantum yields >80%. Compound 2c also showed good emission values in the solid-state due to the push-pull system, supported by the π-π interactions. Compound 1d turned emissive in the solid-state due to the π-π- interactions in the crystal network. This work also confirms that small coumarins derivatives possess photoluminescent properties which can be tuned in both solution and in the solid-state.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules27123677/s1, Figures S1–S16, ¹H and ¹³C NMR spectra; Figure S17, Powder X-ray diffractogram of 1a,b,d; Table S1, HOMO-LUMO interactions of compounds 1b–d, Table S2, HOMO-LUMO interactions of compounds 2b–d.

Author Contributions

Conceptualization, F.J.M.-M., M.R. and N.E.M.-V.; Methodology, C.A.V.-M.; Software, J.P.M.-S. and J.B.-F.; Investigation, I.I.P.-M. and Á.A.R.-O.; Writing, C.A.V.-M., F.J.M.-M. and I.I.P.-M. All authors have read and agreed to the published version of the manuscript.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

Sample Availability

Samples of the compounds 1a–d and 2a–d are available from the authors.

Funding Statement

Partially supported by Universidad de Colima and Consejo Nacional de Ciencia y Tecnología (CONACYT, grants, 316892 and 255354) and SIP-IPN.