New 8-substituted BODIPY-based chromophores: synthesis, optical and electrochemical properties

Nikolay Vologdin; Sylvain Achelle; Sébastien Gauthier; Bertrand Caro; Françoise Robin-le Guen

doi:10.1515/hc-2016-0151

Artikel Open Access

New 8-substituted BODIPY-based chromophores: synthesis, optical and electrochemical properties

Nikolay Vologdin , Sylvain Achelle , Sébastien Gauthier , Bertrand Caro und Françoise Robin-le Guen

Veröffentlicht/Copyright: 17. November 2016

Veröffentlicht von

Veröffentlichen auch Sie bei De Gruyter Brill

Manuskript einreichen Informationen für Autor*innen Erkunden Sie dieses Fachgebiet

Aus der Zeitschrift Heterocyclic Communications Band 22 Heft 6

Abstract

BODIPY-based chromophores, in which an electron withdrawing difluoro-boraindacene fragment is connected via position 8 to different donor fragments, were synthesized. Their electrochemical and photophysical properties were studied. All compounds exhibit a quasi-reversible oxidation corresponding to the formation of a BODIPY π-radical cation at around 0.8 V vs. FeCp₂⁺/FeCp₂ that is slightly sensitive to the nature of the electron donating group. A reversible reduction is observed around−1.6 V vs. FeCp₂⁺/FeCp₂ corresponding to the formation of the BODIPY π-radical anion. Cyclic voltammetry analysis of a γ-methylenepyran substituted BODIPY indicates the formation of redox bistable system with high bistability. In dichloromethane solution, the chromophores exhibit an intense absorption band around 502 nm and an emission in the 516–528 nm range. A significant emission quench is observed in case of amino and γ-methylenepyran substituents.

Keywords: bistable redox systems; BODIPY; fluorescence; Sonogashira reaction

Introduction

Over the past two decades, the difluoroboraindacene (BODIPY) fluorophores have drawn an increased interest due to their unusual properties [1], [2], [3]. The BODIPY derivatives are versatile fluorophores as their properties can easily be tuned by molecular modification [4], [5], [6], [7], [8]. Moreover, the BODIPY fluorophores have robust photophysical properties, such as strong absorption of visible light, high fluorescence quantum yield, good photostability [1], [2], [9], [10] and can be used for numerous applications such as biological labeling and medical imaging [11], [12], [13], [14], photosensitizers for photodynamic therapy [15], molecular switches [16], photovoltaic devices [17], [18], artificial photosynthetic antenna-reaction center assemblies [19] and fluorescent sensors for metal [20], [21], [22], [23] or viscosity [24]. In addition, BODIPY derivatives show amphoteric redox behavior [1], [2]. This property makes the BODIPY fragment an interesting component of organic molecules containing an electron donor and an electron acceptor connected by conjugated bridge. Recently, several articles related to BODIPY-based push-pull systems have been published [25], [26], [27], [28], [29], [30]. In most cases, the 2,6-, 3,5-, and 4,4′-disubstituted molecules have been described, and in these systems, the BODIPY fragment has been used as a bridge between the donor and acceptor parts of the molecule [25], [26], [27], [28] and sometimes as the donor [28] or acceptor part [28], [29], [30]. However, 8-substituted BODIPY compounds in which the difluoroboraindacene fragment acts as the electron-withdrawing part has been less studied [31], [32], [33], [34]. On the basis of these previous results, we have decided to prepare a series of new BODIPY-based dyads in which the electron-withdrawing difluoroboraindacene fragment is connected to different donor fragments via position this paper, we present the synthesis of such molecules and the preliminary studies of their properties.

Results and discussion

Target compounds were obtained by Sonogashira cross-coupling reaction starting from the ethynyl precursor 1 [35] or the iodo analogue 2 [36]. Since, the BODIPY fragment has an electron withdrawing nature, we chose several electron donating groups for the creation of dyads. Thiophene and fluorene derivatives 3 and 4 were obtained by the reaction of substrate 1 and 2-iodothiophene or 2-iodofluorene, respectively, in moderate yield (Scheme 1). Compounds 5–8 were obtained in moderate to good yields starting from iodo derivative 2 (Scheme 2).

Scheme 1

Scheme 2

We were also interested in a similar synthesis of a chromophore bearing a γ-methylenepyran fragment as a proaromatic electron donating part. Indeed, this fragment displays a significantly increased aromatic character upon intermolecular charge transfer (ICT). In this context, the transformations of γ-methylenepyrans to pyryliums upon ICT are particularly attractive as push-pull structures [37], [38]. Moreover, π-conjugated structures incorporating γ-methylenepyran as a building block have been described as interesting redox systems [39], [40]. The chromophore 9 was synthesized by the Sonogashira cross-coupling reaction of 2 and 4-(4-ethynylbenzylidene)-2,6-diphenyl-4H-pyran [41] (Scheme 3).

Scheme 3

All products were characterized by NMR and mass spectroscopy. Unlike the 2,4-methylpyrrole and 1,3,5,7,8-pentamethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene [42] that exhibit proton singlets in their ¹H NMR spectra at 2.09, 2.25 ppm and at 2.41, 2.52 ppm for the protons of methyl groups in position 2,4 and 1,3,5,7, respectively, the molecules 3–9 display signals shifted up-field around 1.4 ppm for the protons of the methyl groups in positions 1,7. Such shielding indicates that the planes of BODIPY and the substituent in position 8 are not coplanar [43]. This geometry favors charge separation and slows down charge recombination that leads to high quantum yields of fluorescence [44].

The electrochemical properties of compounds 3–6 and 8–9 were investigated by cyclic voltammetry in dichloromethane in the presence of NBu₄BF₄ as a supporting electrolyte (Figure 1 and Table 1). The potentials are given in reference to the FeCp₂⁺/FeCp₂ couple.

Figure 1

Cyclic voltammogram of (A) BODIPY 3 and (B) BODIPY 9 dichloromethane in the presence of NBu₄BF₄ (T=293 K, c=2×10^{− 3} M, v=0.1 V×s^{− 1}, working electrode: Pt).

Table 1

Electrochemical data for BODIPY derivatives, (E vs. FeCp₂⁺/FeCp₂) in dichloromethane with NBu₄BF₄ as a supporting electrolyte at 0.1 V×s^{− 1}.

	E_pa(1)^a	E_pa(2)^a	E_1/2(3)^b, (∆E_1/2/mV)	E_pc(4)^c	E_1/2(5)^b(∆E_1/2/mV)
3			0.78 V, (147)		− 1.61 V, (162)
4			0.81 V, (168)		− 1.57 V, (99)
5			0.81 V, (189)		− 1.60 V, (78)
6	0.43 V		0.94 V ^(a)		− 1.56 V, (84)
8			0.90 V, (140)		− 1.59 V, (155)
9		0.40 V	0.87 V, (98)	− 0.81 V	− 1.56 V, (175)

^aIrreversible peak.

^bquasi-reversible peak.

^cIrreversible peak on the reverse cathodic scan.

Compounds 3–5 and 8–9 show a single electrochemically quasi-reversible peak on oxidative scans that is ascribed to the formation of the BODIPY π-radical cation. The oxidation potentials of BODIPY moiety in these compounds are within the same range (0.78 V<E_1/2<0.89 V). On the BODIPY 6 two successive irreversible one-electron oxidation peaks can be resolved and assigned to the oxidation of the dimethylamino group at 0.43 V and the formation of the BODIPY π-radical cation at 0.94 V, respectively. As shown in Table 1 and Figure 1, all compounds 3–6 and 8–9 present a similar single quasi-reversible peak corresponding to the formation of the BODIPY π-radical anion (− 1.61 V<E_1/2 <−1.56 V), on their reduction scans. In addition to the two peaks already observed for the BODIPY fragment 3–5 and 8, the BODIPY fragment of compound 9 containing the γ-methylenepyran fragment also shows an irreversible anodic peak at 0.40 V corresponding to the formation of the pyrylium radical cation 9^+• followed by a dimerization reaction leading to a dipyrylium salt (Table 1 and Figure 1B). The reverse scan exhibits an irreversible cathodic peak at−0.81 V assigned to the reduction of the dipyrylium cation leading to 9 by a C-C cleavage reaction. Both observations are consistent with results previously reported for other methylenepyran derivatives and show the bistability of the redox system (ΔE=1.21 V) [37], [38], [39], [40], [45].

The UV/Vis and photoluminescence (PL) spectroscopic data of BODIPY derivatives 2–9 measured in dichloromethane are presented in Table 2. The spectra of compound 5 are exemplified in Figure 2.

Table 2

Optical spectroscopy data for BODIPY derivatives.

	λ_abs, nm^a (ε, mM−¹×cm−¹)	λ_em, nm^a	ϕ_F^b	Stokes shift, cm−¹
2	269 (5.8), 329 (8.3), 502 (101)	519	0.41	652
3	306 (32.1), 502 (88.4)	519	0.24	652
4	260 (16.7), 318 (57.2), 501 (91.8)	519	0.28	692
5	297 (35.6), 359 (9.1), 502 (89.7)	517	0.27	578
6	258 (22.0), 339 (48.5), 502 (98.0)	516	< 0.01	540
7	353 (46.1), 501 (103)	528	0.06	1021
8	256 (36.2), 316 (43.3), 502 (103)	518	0.28	615
9	281 (43.1), 394 (67.4), 501 (113)	516	< 0.01	580

^aAll spectra were recorded in dichloromethane solutions at room temperature at c=1.0−9.0×10^{− 6} M.

^bFluorescence quantum yield (± 10%) determined relative to 9,10-diphenylethynylanthracene in cyclohexane (Φ_F=1.00) as standard [46].

Figure 2

Absorption (solid line) and emission (dashed line) spectra of compound dichloromethane (c=8.4×10^{− 6} M).

All compounds exhibit a strong S₀-S₁ transition close to 502 nm with high absorption coefficient (88.4–113 mM⁻¹×cm⁻¹) assigned to the boradiazaindacene chromophore [25], [47]. At higher energy, a broad band around 306–394 nm is attributed to the S₀-S₂ transition of the BODIPY moiety [48], [49]. The energy bands at 250–297 nm may be related to the substituted phenylethynyl system [50]. When comparing compounds 3–9 with 1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene, it appears that the addition of donor substituents in position 8 leads to the slight hypsochromic shift of the BODIPY S₀-S₁ transition band (1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (CH₂Cl₂) – 505 nm [51] and compounds 3–9 (CH₂Cl₂) – 502 nm). Neither the nature of the donor substituent nor the nature of the solvent leads to significant changes of the UV/Vis spectra. This feature is characteristic of 8-substituted BODIPY chromophores [52] and can be explained by the decrease of electronic coupling between the donor and acceptor part of molecules in the ground-state configuration due to non-coplanar geometry. All compounds exhibit emission in the range λ=516–528 nm. Compared with unsubstituted BODIPY moieties, the significant emission quenching is observed for all obtained compounds (Φ_F (BODIPY in CH₂Cl₂)=0.80 [53]). Almost total quenching of BODIPY fluorescence is observed in the case of amino derivatives 6 and 7 and pyranylidene chromophore 9. Two different reasons accounting for such fluorescence quenching in the presence of donor substituents have been suggested [32], [52]. First, the twisted intramolecular charge transfer (TICT) is characterized by a dual fluorescence with large Stokes shift, in addition to the emission from the locally excited state [54] and a red shift of the emission band upon transition from a non-polar solvent to a polar solvent [55]. The second reason is the photo-induced electron transfer (PeT) [52]. In our case, the fluorescence quenching is most likely due to PeT because of the absence of dual fluorescence and significant emission solvatochromism observed when the spectra are recorded in n-heptane or acetonitrile (for compound 6, the emission maxima are observed at 518 nm and 514 nm in heptane and acetonitrile, respectively).

Conclusion

Chromophores containing difluoro-boraindacene part as an electron-withdrawing fragment and different electron-donating groups connected with a phenylethynylene bridge via the position 8 of the BODIPY core were synthesized. It was found that BODIPY and the substituent in position 8 are not co-planar. This geometry leads to the decrease of electronic coupling between the donor and the acceptor parts of the molecules in the ground-state configuration. The nature of the donor substituent and the solvent has no influence on UV/Vis spectra of these compounds. On the other hand, the presence of donor substituents causes the fluorescence quenching, probably due to photo-induced electron transfer. Compounds with such properties could be used as fluorescent probes and in light-emitting diodes.

Experimental

All air- and moisture-sensitive reactions were carried out in flame-dried glassware and cooled under nitrogen. ¹H NMR spectra (300 MHz) and ¹³C NMR spectra (75 MHz) were acquired in CDCl₃ at room temperature on a Bruker AC-300 spectrometer (300 MHz). Acidic impurities in CDCl₃ were removed by treatment with anhydrous K₂CO₃. High resolution mass analyses were performed at the ‘Centre Régional de Mesures Physiques de l’Ouest’ (CRMPO, University of Rennes1) on a Bruker MicroTOF-Q II apparatus using ESI/ASAP. UV/vis spectra were recorded with a Uvikon xm Secomam spectrometer using standard 1-cm quartz cells. Fluorescence spectra were recorded using a Spex Fluoro Max-3 Jobin-Y von Horiba apparatus. Compounds were excited at their absorption maxima at the longest-wavelength absorption band. The Φ_F values were calculated using 9,10-diphenylethynylanthracene in cyclohexane as standard [42]. Stokes shifts were calculated by considering the lowest energy absorption band.

General procedures for Sonogashira cross-coupling reaction

Procedure A A mixture of an aryl iodide (1.5 mmol), (Ph₃P)₂PdCl₂ (35 mg, 0.05 mmol, 5% mol.) and CuI (10 mg, 0.05 mmol, 5% mol.) in Et₃N/THF (5 mL/10 mL) was stirred for 15 min and then treated with compound 1 (348 mg, 1 mmol). The mixture was heated to overnight, concentrated and the residue was purified by silica gel column chromatography with the eluent indicated below.

Procedure B A mixture of compound 2 (451 mg, 1.0 mmol), (Ph₃P)₂PdCl₂ (35 mg, 0.05 mmol, 5% mol) and CuI (10 mg, 0.05 mmol, 5% mol.) in 15 mL of diisopropylamine was stirred for 15 min, treated with an arylacetylene (1.2 mmol) and then heated under reflux overnight. After concentration, the residue was purified by column chromatography using the eluent indicated below.

8-(4-(Thiophen-2-ylethynyl)phenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (3) This compounds was obtained using procedure A; chromatography eluent petroleum ether/CH₂Cl₂ (1 : 1); yield 244 mg (57%); mp>260°C; ¹H NMR: δ 1.43 (s, 6H); 2.56 (s, 6H); 5.99 (s, 2H); 7.04 (dd, 1H, J₁=3.8 Hz, J₂=5.1 Hz); 7.28 (d, 2H, J=8.5 Hz); 7.32–7.35 (m, 2H); 7.64 (d, 2H, J=8.5 Hz); NMR: δ 14.6 (CH₃), 84.1 (C), 92.3 (C), 121.4 (CH), 122.8 (C), 123.9 (C), 127.2 (CH), 127.8 (CH), 128.3 (CH), 132.1 (CH), 132.3 (CH), 135.1 (C), 140.8 (C), 143.0 (C), 155.8 (C). HR-MS. Calcd for C₂₅H₂₂¹¹BF₂N₂S [M + H] ⁺: m/z 431.1559. Found: m/z 431.1560.

8-(4-(9H-Fluoren-2-yl)phenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (4) This compound was obtained using procedure A; chromatography eluent petroleum ether/AcOEt (3 : 2 to 1 : 1); yield 179 mg (35%); mp>260°C; ¹H NMR: δ 1.45 (s, 6H); 2.56 (s, 6H); 3.94 (s, 2H); 6.00 (s, 2H); 7.29 (d, 2H, J=8.1 Hz); 7.32–7.45 (m, 3H); 7.56–7.60 (m, 2H); 7.68 (d, 2H, J=8.1 Hz); 7.74–7.81 (m, 2H); NMR: δ 13.6 (CH₃), 35.8 (CH₂), 87.6 (C), 90.6 (C), 118.9 (CH), 119.3 (CH), 119.8 (C), 120.4 (CH), 123.4 (C), 124.1 (CH), 126.0 (CH), 126.3 (CH), 127.3 (CH), 129.6 (CH), 131.3 (CH), 133.8 (C), 134.1 (CH), 139.9 (C), 140.0 (C), 141.3 (C), 142.1 (C), 142.3 (C), 142.6 (C), 154.8 (C). HR-MS. Calcd for C₃₄H₂₈¹¹BF₂N₂ [M + H] ⁺: m/z 513.2308. Found: m/z 513.2306.

8-(4-(4-Methoxyphenylethynyl)phenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (5) This compound was obtained using procedure B; chromatography eluent petroleum ether/AcOEt (9 : 1); yield 377 mg (83%); mp>260°C; ¹H NMR: δ 1.43 (s, 6H); 2.56 (s, 6H); 3.84 (s, 3H); 5.99 (s, 2H); 6.90 (d, 2H, J=8.7 Hz); 7.28 (d, 2H, J=8.7 Hz); 7.49 (d, 2H, J=8.7 Hz); 7.64 (d, 2H, J=8.7 Hz); NMR: δ 14.6 (CH₃), 55.3 (CH₃), 87.4 (C), 90.9 (C), 114.1 (CH), 114.9 (C), 121.3 (CH), 124.5 (C), 128.2 (CH), 131.3 (C), 132.1 (CH), 133.1 (CH), 134.6 (C), 141.0 (C), 155.7 (C), 160.0 (C). HR-MS. Calcd for C₂₈H₂₅¹¹BF₂KN₂O [M + K] ⁺: m/z 493.1660. Found: m/z 493.1659.

8-(4-(4-N,N-Dimethylaminophenylethynyl)phenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (6) This compound was obtained using procedure B; chromatography eluent petroleum ether/CH₂Cl₂ (1 : 1 to pure CH₂Cl₂); yield 327 mg (70%); mp>260°C; ¹H NMR: δ 1.44 (s, 6H); 2.55 (s, 6H); 3.00 (s, 6H); 5.98 (s, 2H); 6.67 (d, 2H, J=8.7 Hz); 7.24 (d, 2H, J=8.7 Hz); 7.42 (d, 2H, J=8.7 Hz); 7.62 (d, 2H, J=8.7 Hz); NMR: δ 14.6 (CH₃), 40.2 (CH₃), 86.8 (C), 92.3 (C), 109.4 (C), 111.8 (CH), 121.3 (CH), 125.1 (C), 128.1 (CH), 131.3 (C), 131.9 (CH), 132.8 (CH), 134.0 (C), 141.2 (C), 150.3 (C), 155.6 (C). HR-MS. Calcd for C₂₉H₂₈¹¹BF₂KN₃ [M + K] ⁺: m/z 506.1876. Found: m/z 506.1979.

8-(4-(4-N,N-Diphenylaminophenylethynyl)phenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (7) This compound was obtained using procedure B; chromatography eluent petroleum ether/CH₂Cl₂ (1 : 1); yield 219 mg (37%); mp>260°C; ¹H NMR: δ 1.44 (s, 6H); 2.55 (s, 6H); 5.99 (s, 2H); 7.02 (d, 2H, J=8.7 Hz); 7.14–7.05 (m, 6H); 7.32–7.27 (m, 6H); 7.39 (d, 2H, J=8.7 Hz); 7.63 (d, 2H, J=8.7 Hz); NMR: δ 14.6 (CH₃), 87.9 (C), 91.2 (C), 115.4 (C), 121.3 (CH), 122.0 (CH), 123.7 (CH), 124.5 (C), 125.1 (CH), 128.2 (CH), 129.4 (CH), 132.1 (CH), 132.6 (CH), 134.5 (C), 143.0 (C), 147.1 (C), 148.3 (C), 155.7 (C). HR-MS. Calcd for C₃₉H₃₂¹¹BF₂KN₃ [M + K] ⁺: m/z 630.2289. Found: m/z 630.2291.

8-(4-((6-Methoxynaphthalen-2-yl)ethynyl)phenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (8) This compound was obtained using procedure B; chromatography eluent petroleum ether/CH₂Cl₂ (7 : 3 to 1 : 1); yield 383 mg (76%); mp>260°C; ¹H NMR: δ 1.44 (s, 6H); 2.55 (s, 6H); 3.93 (s, 3H); 5.98 (s, 2H); 7.18–7.12 (m, 2H); 7.28 (d, 2H, J=8.7 Hz); 7.55 (dd, 1H, J₁=8.7 Hz, J₂=1.5 Hz ); 7.68 (d, 2H, J=8.7 Hz), 7.74–7.72 (m, 2H), 7.94 (s, 1H); NMR: δ 14.6 (CH₃), 53.4 (CH₃), 88.3 (C), 91.4 (C), 105.9 (CH), 117.7 (C), 119.6 (CH), 121.4 (CH), 124.4 (C), 127.0 (CH), 128.2 (CH), 128.5 (C), 129.4 (CH), 131.5 (CH), 132.3 (CH), 134.4 (C), 134.8 (C), 143.0 (C), 155.8 (C), 158.5 (C). HR-MS. Calcd for C₃₂H₂₇¹¹BF₂KN₂O [M + K] ⁺: m/z 543.1816. Found: m/z 543.1815.

8-(4-((4-((2,6-Diphenyl-4H-pyran-4-ylidene)methyl)phenyl)ethynyl)phenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (9) This compound was obtained using procedure B (a mixture of THF/NEt₃ was used as solvent instead of HNiPr₂); chromatography eluent petroleum ether/CH₂Cl₂ (3 : 2 to 2 : 3); yield 341 mg (51%); mp>260°C; ¹H NMR: δ 1.45 (s, 6H); 2.57 (s, 6H); 5.93 (s, 1H); 6.00 (s, 2H); 6.44 (s, 1H); 7.02 (s, 1H); 7.29 (d, 2H, J=8.3 Hz); 7.38–7.46 (m, 8H); 7.53 (d, 2H, J=8.3 Hz); 7.67 (d, 2H, J=8.3 Hz); 7.75–7.82 (m, 4H); NMR: δ 14.6 (CH₃), 88.9 (C), 91.4 (C), 102.0 (CH), 108.6 (CH), 113.5 (CH), 119.3 (C), 121.3 (CH), 124.4 (C), 124.6 (CH), 125.0 (CH), 127.6 (CH), 128.2 (CH), 128.7 (CH), 130.4 (C), 131.8 (CH), 132.2 (CH), 133.2 (C), 133.4 (C), 134.8 (C), 139.1 (C), 141.0 (C), 143.0 (C), 151.2 (C), 153.2 (C), 155.7 (C). HR-MS. Calcd for C₄₅H₆₆¹¹BF₂N₂O [M + H] ⁺: m/z 669.2883. Found: m/z 669.2866.

Supporting information

¹H NMR and ¹³C NMR spectra of compounds 3–9, UV/Vis and emission spectra of compounds 2–9 in dichloromethane, emission spectra of compound 7 in heptane and MeCN can be found in the online supplement.

Acknowledgments

Nikolay Vologdin thanks the region Bretagne for a post-doctoral fellowship. Conseil Régional de Bretagne.

References

[1] Ulrich, G.; Ziessel, R.; Harriman, A. The chemistry of fluorescent BODIPY dyes: versatility unsurpassed. Angew. Chem. Int. Ed.2008, 47, 1184–1201.10.1002/anie.200702070Suche in Google Scholar PubMed

[2] Ziessel, R. Reflets d’un chimie largement inexplorée: celle des boradipyrrométhènes. C. R. Chimie2007, 10, 622–629.10.1016/j.crci.2007.04.003Suche in Google Scholar

[3] Bañuelos, J. BODIPY dye, the most versatile fluorophore ever? Chem. Rec.2016, 16, 335–348.10.1002/tcr.201500238Suche in Google Scholar PubMed

[4] Boens, N.; Verbelen, B.; Dehaen, W. Postfunctionalization of the BODIPY Core: synthesis and spectroscopy. Eur. J. Org. Chem.2015, 6577–6595.10.1002/ejoc.201500682Suche in Google Scholar

[5] Niu, S.; Ulrich, G.; Retailleau, P.; Harrowfield, J.; Ziessel, R. New insights into the solubilization of BODIPY dyes. Tetrahedron Lett.2009, 50, 3840–3844.10.1016/j.tetlet.2009.04.017Suche in Google Scholar

[6] Palma, A.; Tasior, M.; Frimannsson, D. O.; Vu, T. T.; Meallet-Renault, R.; O’Shea, D. F. New on-bead near-infrared fluorophores and fluorescent sensor constructs. Org. Lett.2009, 11, 3638–3641.10.1021/ol901413uSuche in Google Scholar PubMed

[7] Bonardi, L.; Ulrich, G.; Ziessel, R. Tailoring the properties of boron-dipyrromethene dyes with acetylenic functions at the 2,6,8 and 4-b substitutions positions. Org. Lett.2008, 10, 2183–2186.10.1021/ol800560bSuche in Google Scholar PubMed

[8] Loudet, A.; Burgess, K. BODIPY dyes and their derivatives: syntheses and spectroscopic properties. Chem. Rev. 2007, 107, 4891–4932.10.1142/9789814307246_0009Suche in Google Scholar

[9] Ziessel, R.; Harriman, A. Artificial light-havesting antennae: electronic energy transfer by way of molecular funnels. Chem. Commun. 2011, 47, 611–631.10.1039/C0CC02687ESuche in Google Scholar

[10] Chen, Y.; Zhao, J.; Guo, H.; Xie, L. Geometry relaxation-induced large stokes shift in red-emitting borondipyrromethenes (BODIPY) and applications in fluorescent thiol probes. J. Org. Chem.2012, 77, 2192–2206.10.1021/jo202215xSuche in Google Scholar PubMed

[11] Kawada, T.; Maeda, H.; Kikuchi, K. BODIPY-based probes for the fluorescence imaging of biomolecules in living-cells. Chem. Soc. Rev.2015, 44, 4953–4972.10.1039/C5CS00030KSuche in Google Scholar

[12] Niu, S. L.; Massif, C.; Ulrich, G.; Renard, P.-Y.; Romieu, A.; Ziessel, R. Water-Soluble Red-Emitting Distyryl-Borondipyrromethene (BODIPY) Dyes for Biolabeling. Chem. Eur. J.2012, 18, 7229–7242.10.1002/chem.201103613Suche in Google Scholar PubMed

[13] Niu, S. L.; Massif, C.; Ulrich, G.; Ziessel, R.; Romieu, A.; Renard, P.-Y. Water-solubilisation and bio-conjugation of a red-emitting BODIPY marker. Org. Biomol. Chem.2011, 9, 66–69.10.1039/C0OB00693ASuche in Google Scholar

[14] Maindron, N.; Ipuy, M.; Bernhard, C.; Lhenry, D.; Moreau, M.; Carme, S.; Oudot, A.; Collin, B.; Vrigneaud, J.-M.; Provent, P.; et al. Near-infrared-emitting BODIPY-trisDOTA¹¹¹In as a monomolecular multifunctional imaging probe: from synthesis to in vivo investigations. Chemistry2016, 22, 12670–12674.10.1002/chem.201602886Suche in Google Scholar PubMed

[15] Kamkaew, A.; Lim, S. H.; Lee, H. B.; Kiew, L. V.; Chung, L. Y.; Burgess, K. BODIPY dyes in photodynamic therapy. Chem. Soc. Rev.2013, 42, 77–88.10.1039/C2CS35216HSuche in Google Scholar PubMed PubMed Central

[16] Mukherjee, S.; Thilagar, P. Fine-Tuning dual emission and aggregation-induced emission switching in NPI-BODIPY dyads. Chem. Eur. J.2014, 20, 9052–9062.10.1002/chem.201305049Suche in Google Scholar PubMed

[17] Mao, M.; Zhang, X. L.; Cao, L.; Tong, Y.; Wu, G. H. Design of BODIPY based organic dyes for high-efficient dyes sensitized solar cells employing double electron acceptors. Dyes Pigm.2015, 117, 28–36.10.1016/j.dyepig.2015.02.001Suche in Google Scholar

[18] Bessette, A.; Hanan, G. S. Design, synthesis and photophysical studies of dipyrromethene-based materials: insights into their applications in organic photovoltaic devices. Chem. Soc. Rev.2014, 43, 3342–3405.10.1039/C3CS60411JSuche in Google Scholar

[19] Liu, J.-Y.; Yeung, H.-S.; Xu, W.; Li, X.; Ng, D. K. P. Highly Efficient Energy Transfer in Subphthalocyanine-BODIPY Conjugates. Org. Lett.2008, 10, 5421–5424.10.1021/ol8023677Suche in Google Scholar PubMed

[20] Richards, G. J.; Gobo, Y.; Yamamura, M.; Nabeshima, T. Biphenyl appendend BODIPY derivatives showing combined environmental polarity and heavy metal cation sensing functionality. New J. Chem.2015, 39, 5886–5889.10.1039/C5NJ00611BSuche in Google Scholar

[21] Kim, H. N.; Ren, W. X.; Kim J. S.; Yoon, J. Fluorescent and colorimetric sensors for detection of lead, cadmium, and mercury ions. Chem. Soc. Rev. 2012, 41, 3210–3244.10.1039/C1CS15245ASuche in Google Scholar

[22] Kursunlu, A. N.; Guler, E.; Ucan, H. I.; Boyle, R. W. A novel BODIPY-Dipyrrin fluorescent probe: synthesis and recognition behaviour towards Fe (II) and Zn (II). Dyes Pigm.2012, 94, 496–502.10.1016/j.dyepig.2012.02.006Suche in Google Scholar

[23] Kursunlu, A. N.; Deveci, P.; Guler, E. Synthesis and spectroscopic-electrochemical properties of novel ratiometric Hg (II) chemosensor containing BODIPY and the N-phenylaza-15-crown-5 moiety. J. Lumin.2013, 136, 430–436.10.1016/j.jlumin.2012.12.020Suche in Google Scholar PubMed PubMed Central

[24] Xochitiotzi-Flores, Z.; Jiménez-Sánchez, A.; García-Ortega, H.; Sánchez-Puig, N.; Romero-Ávila, M.; Santillan, R.; Farfán, N. Optical properties of two fluorene derived BODIPY molecular rotors as fluorescent ratiometric viscosity probes. New J. Chem.2016, 40, 4500–4512.10.1039/C5NJ03339JSuche in Google Scholar

[25] Ulrich, G.; Barsella, A.; Boeglin, A.; Niu, S.; Ziessel, R. BODIPY-Bridged push-pull chromophores for nonlinear optical applications. ChemPhysChem2014, 15, 2693–2700.10.1002/cphc.201402123Suche in Google Scholar PubMed

[26] Shi, W.-J.; Lo, P.-C.; Singh A.; Ledoux-Rak, I.; Ng, D. K. P. Synthesis and second-order nonlinear optical properties of push-pull BODIPY derivatives. Tetrahedron2012, 68, 8712–8718.10.1016/j.tet.2012.08.033Suche in Google Scholar

[27] Niu, S.; Ulrich, G.; Retailleau, P.; Ziessel, R. BODIPY-bridged push-pull chromophores optical and electrochemical properties. Tetrahedron Lett. 2011, 52, 4848–4853.10.1016/j.tetlet.2011.07.028Suche in Google Scholar

[28] Xiao, L.; Wang, H.; Gao, K.; Li, L.; Liu, C.; Peng, X.; Wong, W.-Y.; Wong, W.-K.; Zhu, X. A-D-A type small molecules based on boron dipyrromethene for solution-processed organic solar cells. Chem. Asian J. 2015, 10, 1513–1518.10.1002/asia.201500382Suche in Google Scholar PubMed

[29] Debnath, S.; Singh, S.; Bedi, A.; Krishnamoorthy, K.; Zade, S. S. Synthesis, optoelectronic adn transistor properties of BODIPY- and Cyclopenta[c]thiophene-containing Π-conjugated copolymers. J. Phys. Chem. C2015, 119, 15859–15867.10.1021/acs.jpcc.5b02743Suche in Google Scholar

[30] Nano, A.; Ziessel, R.; Stachelek, P.; Harriman, A. Charge-recombination fluorescence from push-pull electronic systems constructed around amino-substituted styryl-BODIPY Dyes. Chem. Eur. J. 2013, 19, 13528–13537.10.1002/chem.201301045Suche in Google Scholar PubMed

[31] Heyer, E.; Ziessel, R. Step-by-step synthesis of multimodule assemblies engineered from BODIPY, DPP, and Triphenylamine Moieties. J. Org. Chem. 2015, 80, 6737–6753.10.1021/acs.joc.5b00917Suche in Google Scholar PubMed

[32] Collado, D.; Casado, J.; Rodríguez González, S.; López Navarrete, J. T.; Suau, R.; Pérez-Inestrosa, E.; Pappenfus,T. M.; Raposo, M. M. M. Enhanced functionality for donor-acceptor oligothiophenes by means of inclusion of BODIPY: synthesis, eelctrochemistry, photophysics, and model chemistry. Chem. Eur. J.2011, 17, 498–507.10.1002/chem.201001942Suche in Google Scholar PubMed

[33] Roacho, R. I.; Metta-Magaña, A. J.; Peña-Cabrera, E.; Pannell, K. H. Synthesis, structural characterization, and spectroscopic properties of the ortho, meta and para isomers of 8-(HOCH₂-C₆H₄)-BODIPY and 8-(MeOC₆H₄)-BODIPY. J. Phys. Org. Chem. 2013, 26, 345–351.10.1002/poc.3095Suche in Google Scholar

[34] Hu, R.; Lager, E.; Aguilar-Aguilar, A.; Liu, J.; Lam, J. W. Y.; Sung, H. H. Y.; Williams, I. D.; Zhong, Y.; Wong, K. S.; Peña-Cabrera, E.; et al. Twisted intramolecular charge transfer and agrregation-induced emission of BODIPY derivatives. J. Phys. Chem. C2009, 113, 15845–15853.10.1021/jp902962hSuche in Google Scholar

[35] Li, Z.; Bittman, R. Synthesis and spectral properties of cholesterol- and FTY720-containing boron dipyrromethene dyes. J. Org. Chem. 2007, 72, 8376–8382.10.1021/jo701475qSuche in Google Scholar PubMed PubMed Central

[36] Tahtaoui, C.; Thomas, C.; Rohmer, F.; Klotz, P.; Duportail, G.; Mely, Y.; Bonnet, D.; Hibert, M. Convenient method to access new 4,4-dialkoxyl- and 4,4-diaryloxy-diaza-s-indacene dyes: synthesis and spectroscopic evaluation. J. Org. Chem. 2007, 72, 269–272.10.1021/jo061567mSuche in Google Scholar PubMed

[37] Achelle, S.; Malval, J.-P.; Aloïse, S.; Barsella, A.; Spangenberg, A.; Mager, L.; Akdas-Kilig, H.; Fillaut, J.-L.; Caro, B.; Robin-le Guen, F. Synthesis, photophysics and nonlinear optical properties of stilbenoid pyrimidine-based dyes bearing methylenepyran donor groups. ChemPhysChem2013, 14, 2725–2736.10.1002/cphc.201300419Suche in Google Scholar PubMed

[38] Andreu, R.; Galan, E.; Orduna, J.; Villacampa, B.; Alicante, R.; Lopez Navarrete, J.-T.; Casado, J.; Garin, J. Aromatic/proaromatic donors in 2-dicyanomethylenthiazole merocyanines: from neutral to strongly zwitterionic nonlinear optical chromophores. Chem. Eur. J.2011, 17, 826–838.10.1002/chem.201002158Suche in Google Scholar PubMed

[39] Ba, F.; Cabon, N.; le Poul, P.; Kahlal, S.; Saillard, J.-Y.; le Poul, N.; Golhen, S.; Caro, B.; Robin-le Guen, F. Diferrocenylpyrylium salts and electron rich bispyran from oxidative coupling of ferrocenylpyran. Example of redox systems switched by proton trasnfer. New J. Chem.2013, 37, 2066–2081.10.1039/c3nj41126eSuche in Google Scholar

[40] Ba, F.; Cabon, N.; Robin-le Guen, F.; le Poul, P.; le Poul, N.; le Mest, Y.; Golhen, S.; Caro, B. Differocenylbispyrylium salts and electron-rich diferrocenylbispyran from oxidative coupling of ferrocenylpyran. Induced electron transfer C-C bond making/breaking involving a metallocenyl radical intermediate. Organometallics2008, 27, 6396–6399.10.1021/om800638qSuche in Google Scholar

[41] Gauthier, S.; Vologdin, N.; Achelle, S.; Barsella, A.; Caro, B.; Robin-le Guen, F. Methylenepyran based dipolar and quadrupolar dyes: synthesis, electrochemical and photochemical properties. Tetrahedron2013, 69, 8392–8399.10.1016/j.tet.2013.07.066Suche in Google Scholar

[42] Nepomnyashchii, A. B.; M. Bröring, M.; Ahrens, J.; Bard, A. J. Synthesis, photophysical, eelctrochemical, and eelctrogenerated chemiluminescence studies. multiple sequential eelctron transfer in BODIPY monomers, dimers, trimers and polymer. J. Am. Chem. Soc.2011, 133, 8633–8645.10.1021/ja2010219Suche in Google Scholar PubMed

[43] Nöll, G.; Daub, J.; Lutz, M.; Rurack, K. Synthesis, spectroscopic properties, and electropolymerization of azulene dyads. J. Org. Chem.2011, 76, 4859–4873.10.1021/jo200080vSuche in Google Scholar PubMed

[44] Rurack, K.; Kollmannsberger, M.; Resch-Genger, U.; Daub, J. A selective and sensitive fluoroionophore for Hg^II, Ag^I and Cu^II with virtually decoupled fluorophore and receptor units. J. Am. Chem. Soc.2000, 122, 968–969.10.1021/ja992630aSuche in Google Scholar

[45] Vologdin, N.; Gauthier, S. Achelle, S. Caro, B.; Robin-le Guen, F. Synthesis of bromo- adn carboxylic acid-substituted methylenepyrans. Lett. Org. Chem. 2014, 11, 606–614.10.2174/1570178611666140512210227Suche in Google Scholar

[46] Eaton, D. F. Reference materials for fluorescence measurement. Pure Appl. Chem.1988, 60, 1107–1114.10.1351/pac198860071107Suche in Google Scholar

[47] Qin, W.; Baruah, M.; Van der Auwereraer, M; De Schryver, F. C.; Boens, N. Photophysical properties of borondipyrromethene analogues in solution. J. Phys. Chem. A2005, 109, 7371–7384.10.1021/jp052626nSuche in Google Scholar PubMed

[48] Qin, W.; Rohand, T.; Baruah, M.; Stefan, A.; van der Auweraer, M.; Dehaen, W.; Boens, N. Solvent-dependant photophysical properties of borondipyrromethene dyes in solution. Chem. Phys. Lett. 2006, 420, 562–568.10.1016/j.cplett.2005.12.098Suche in Google Scholar

[49] Karolin, J.; Johansson, L. B. Å.; Strandberg, L.; Ny, T. Fluorescence and absorption spectroscopic properties of dipyrrometheneboron difluoride (BODIPY) derivatives in liquids, lipid membranes and proteins. J. Am. Chem. Soc.1994, 116, 7801–7806.10.1021/ja00096a042Suche in Google Scholar

[50] Wan, C. W.; Burghart, A.; Chen, J.; Berström F.; Johansson, L. B. Å.; Wolford, M. F.; Kim, T. G.; Topp, M. R.; Hochstrasser, R. M.; Burgess, K. Anthracene-BODIPY cassette: syntheses and energy transfer. Chem. Eur. J. 2003, 9, 4430–4441.10.1002/chem.200304754Suche in Google Scholar PubMed

[51] Wu, L.; Burgess, K. A new synthesis of symmetric boroindacene (BODIPY) dyes. Chem. Commun. 2008, 4933–4935.10.1039/b810503kSuche in Google Scholar PubMed

[52] Sunahara, H.; Urano, Y.; Kojima, H.; Nagano, T. Design and synthesis of a library of BODIPY-based environmental polarity sensors utilizing photoinduced electron-transfer-controlled fluorescence ON-OFF switching. J. Am. Chem. Soc. 2007, 129, 5597–5604.10.1021/ja068551ySuche in Google Scholar PubMed

[53] Shah, M.; Thangaraj, K.; Soong, M. L.; Wolford, L.; Boyer, J. H.; Politzer, I. R.; Pavlopoulos, T. G. Pyrromethene-BF₂ complexes as laser dyes: 1. Heteroatom Chem. 1990, 1, 389–399.10.1002/hc.520010507Suche in Google Scholar

[54] Kim, Y. H.; Cho, D. W.; Yoon, M. Observation of hydrogen-bonding effects on twisted intramolecular charge transfer of p-(n,n-diethylamino)benzoic acid in aqueous cyclodextrin solutions. J. Phys. Chem. 1996, 100, 15670–15676.10.1021/jp9613652Suche in Google Scholar

[55] Shen, P.; Xiao, S.; Zhan, X.; Zhang, W.; Chang, K.; Yang, C. A new pH fluorescent switch by modulation of twisted intramolecular charge transfer with protonation. J. Phys. Org. Chem. 2013, 26, 858–862.10.1002/poc.3185Suche in Google Scholar

Supplemental Material:

The online version of this article (DOI: 10.1515/hc-2016-0151) offers supplementary material, available to authorized users.

Received: 2016-7-17

Accepted: 2016-9-12

Published Online: 2016-11-17

Published in Print: 2016-12-1

This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

Supplementary material

Artikel in diesem Heft

https://doi.org/10.1515/hc-2016-0151

Schlagwörter für diesen Artikel

bistable redox systems; BODIPY; fluorescence; Sonogashira reaction

Creative Commons

BY-NC-ND 3.0

New 8-substituted BODIPY-based chromophores: synthesis, optical and electrochemical properties

Artikel

Abstract

Introduction

Results and discussion

Conclusion

Experimental

General procedures for Sonogashira cross-coupling reaction

Supporting information

Acknowledgments

References

Supplemental Material:

Zusatzmaterial

Artikel in diesem Heft

Artikel in diesem Heft

Artikel in diesem Heft