Light-Driven Molecular Dynamics in Perylenes with Medium

Subscriber access provided by IDAHO STATE UNIV

Article

Light-driven Molecular Dynamics in Perylenes with Medium-controlled Emission Heinz Langhals, Robert Greiner, Thorben Schlücker, and Andreas C. Jakowetz J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00409 • Publication Date (Web): 29 Mar 2019 Downloaded from http://pubs.acs.org on March 29, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Organic Chemistry

Light-driven Molecular Dynamics in Perylenes with Medium-controlled Emission Heinz Langhals,* Robert Greiner, Thorben Schlücker and Andreas C. Jakowetz Department of Chemistry, LMU University of Munich, Butenandtstraße 13, D-81377 Munich, Germany *E-Mail: [email protected]

KEYWORDS: Fluorescence • Molecular dynamics • PLICT • Stokes' shift • Solvatochromism ABSTRACT: Highly fluorescent light emitters with medium-tunable clear colors were obtained from the skeleton of perylenedicarboximide by the attachment of donor-substituted aryl groups in peri-position. The 4-methoxynaphthyl derivative 3a is preferred because of its strong solvatochromism in fluorescence where a mechanism of incomplete PLICT is made responsible both for the large Stokes' shift and the strong medium influence on fluorescence allowing the fine tuning of colour. Introduction High fluorescence quantum yields of organic materials1-5 can be expected for firm, rigid structures such as perylene dyes6-8 where a similar geometry and electron distribution in the ground and the excited state cause small Stokes’ shifts and strong spectral overlap between UV/Vis absorption and fluorescence spectra. On the other hand, the spectral overlap causes re-absorption of the fluorescence light weakening the optical impression of fluorescence and downgrading the efficiencies for many applications such as for illumination, analytics, lasers9-

ACS Paragon Plus Environment

The Journal of Organic Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 17

2 11

and solar light collectors.12-17 Flexible structures may be useful to increase the Stokes’ shift.

However, this leads to a balancing act because of fluorescence quenching according to the loose bolt mechanism defined by Lewis and Calvin.18-21 Sterical restriction of rotation (SRR) is an appropriate concept for the preservation of high fluorescence quantum yields where large Stokes’ shifts could be realized by means of the dynamics of the dihedral angle around a single bond between two chromophores; SRR was achieved by single bonds to 1-naphthalene substructures where hydrogen atoms in the peri-position hindered free rotation. However, comparable large systems were required where the Stokes’ shift is essentially determined by molecular properties.22 A realization with smaller molecules and the possibility of tuning the optical properties would bring about an appreciable progress; large, tunable Stokes’ shifts were found23 for the UV light-absorbing naphthalimids with aryl donor groups in periposition.

Figure 1. Schematic of an interconnected electron donor and acceptor with vertical optical excitation (h) as the first step. Subsequent relaxation may either proceed with tendency for planarisation according to the PLICT16,24 mechanism (upper path) or for orthogonalisation according to the TICT25-27 mechanism (lower path).

We attributed this special spectral behavior to an incomplete PLICT16,24 (planarized intramolecular charge transfer) mechanism according to Figure 1 because of the observed comparably high fluorescent quantum yields; this excludes a TICT mechanism25-27 (twisted intramolecular charge transfer) as an alternative where even fluorescence quenching was observed as a consequence of sterically locked orthogonalisation.23


Page 3 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


3 Results and discussion Chart 1. Perylene carboximides with peri-arylsubstituents

O aryl

9

R N

10

H

O

1

Here we targeted chromophores for such dynamic operating in the visible where perylene carboximides28 1 form attractive basic structures. A linking in position 9 with electron rich aryl groups is expected to effectuate SRR by the peri-situated hydrogen atom in position 10.

Scheme 1. Synthesis of the 9-arylperylene-3,4-dicarboximides 3; 3a: aryl = 4methoxynaphth-1-yl, 91 % yield, R-R = -C(CH3)2C(CH3)2-; 3b: aryl = 3,4,5trimethoxyphenyl, 94% yield, R = H. i) Pd(P(C6H5)3)4, toluene, ethanol/water, 80°C, 17 h.

RO B

O Br

aryl

O

RO

aryl N

N i)

O

O

2

3

Thus, the starting material for synthesis was bromoperylenecarboximide28 2 and allowed the reaction with electron rich aryl dioxaboralanes according to the Suzuki cross coupling to obtain 3 where the long-chain secondary N substituent 1-hexylheptyl (swallow-tail substituent) effectuates the necessary solubility5-7 in lipophilic media; see Scheme 1. We introduced a 4-methoxy-1-naphthyl group as the aryl group in 3a and a 2,4,6trimethoxyphenyl group in 3b because these substituents caused most pronounced Stokes'



Page 4 of 17

4 shifts and solvatochromism in the series of the corresponding more hypsochromically absorbing naphthalenecarboximides.23 Both derivatives could be isolated in high yields (91 % for 3a and 94 % for 3b) and form stable red powders. absorption

fluorescence

1.0

1.0 I

E

0.5

0.5

0.0 300

0.0 400

500

600

 in nm

700

Figure 2. UV/Vis absorption (left) and fluorescence spectra (right) of 3a exhibiting strong solvatochromism in fluorescence; solvents from left to right: n-Heptane (solid curves), toluene (dashed blue curves), chloroform (dotted, magenta) and ethanol (dotted dashed, red).

Table 1. Solvatochromism of the fluorescence of 3a and 3b (max). Molar energies of fluorescence: ET = 28591 kcal·nm·mol-1 / max. Fluorescence quantum yields . Fluorescence lifetimes  with 1 and 2 for bi-exponential decay (the lifetimes of bi-exponential decays slightly depend on the range of data collection, however, are reproducible under identical conditions). The ET(30) solvent polarity scale29-31 as the reference for indicating the dipolarity of a solvent. Solvent

Heptane

ET(30)

max(3a)

ET(3a)

o(3a)

Stokes' shift

 a

max(3b)

ET(3b)

(3b)

Stokes' shift

kcal/mol

nm

kcal/mol

%

eV

ns

Nm

kcal/mol

%

eV

52.6

54.4b

53.34

53.9b

0.13

3.83

0.16

4.05

536.5

53.29

60.2b

0.12

4.03

31.1

543.5

0.17

3.92

536

 a

Cyclohexane

30.9

543.5

52.6

61.3b

Toluene

33.9

571.5

50.0

60.9

0.24

4.28

556

51.42

60.7

0.17

4.27

1,4-dioxane

36.0

574

49.8

56.7

0.27

4.42

558

51.24

57.7

0.20

4.43

THF

37.4

598

47.8

53.8

0.36

4.39

579

49.38

55.9

0.28

4.31

Chloroform

39.1

608.5

47.0

52.4

0.36

4.34

580

49.29

57.2

0.27

4.83

DMF

43.2

644

44.4

24.6

0.51

2.59, 9.8

616

46.41

6.3

0.40

0.70, 8.1

DMSO

45.1

652

43.9

12.2

0.51

1.68, 7.4

619

46.19

4.3

0.40

0.53. 6.4

Acetonitrile

45.6

636

45.0

31.6

0.50

3.45

606

47.18

8.3

0.40

0.89. 9.4


Page 5 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


5 1-butanol

49.7

637

44.9

35.4

0.48

3.52

616

46.41

33.4

0.41

3.05

Ethanol

51.9

648

44.1

23.2

0.53

2.74, 9.6

618

46.26

15.9

0.43

1.68, 22

Methanol

55.4

657

43.5

8.3

0.57

0.96, 5.1

623

45.89

3.2

0.46

0.44, 4.8

a) Fluorescence lifetimes; only 1 if mono exponential, 1, 2 if bi exponential. b) Limited precision because of spectral overlap.

The dyes 3 are highly fluorescent in solution; a fluorescence quantum yield of 54 % was found for 3a in heptane. The dyes exhibit a moderate solvatochromism in UV/Vis absorption and a strong solvatochromism in fluorescence; see Figure 2 and Table 1. The extent of solvent influence was estimated by means of a linear correlation of their ET values (see Table 1) with the ET(30) polarity scale29-31 providing a good blend of chemical dipolarity according to ref.23 where polar protic solvents were excluded because of specific solvent interactions. An absolute larger slope was obtained for 3a (a = -0.6) than for 3b (a = -0.5) where the effect is slightly below half the effect of the extraordinarily strong solvatochromic analogous naphthalene derivatives.23 Obviously, steric interactions of the hydrogen atoms in the peripositions in 3a cause stronger effects (SRR) than the synergetic electron release of three neighboured methoxy groups in 3b. As a consequence, we focussed on the stronger solvatochromic 3a in the subsequent sections. Moreover, 3a and 3b exhibit large Stokes' shifts where mechanisms of incomplete PLICT were made responsible for (i-PLICT).

Figure 3. Increasing the Stokes' shift by incomplete PLICT of 3a (R = CH(C6H13)2) starting with the electronic ground state (upper left), vertical electronic excitation (to upper right), relaxation including the solvent shell (to lower right), fluorescence (to lower left) and second relaxation to the initial state.



Page 6 of 17

6 O O

CH3

R N O

O

R N O

CH3

R N O

relaxation O

*

O h

relaxation

CH3 O

O -h'

CH3 O

*

R N O

This is indicated in Figure 3 for 3a beginning with the vertical optical excitation of the electronic ground state from upper left to upper right. The subsequent relaxation of the electronically excited state comprises both a conjugation-induced partial planarisation against the steric repulsion of the hydrogen atoms in the peri-positions and the relaxation of the solvent shell where the solvent polarity32 becomes basically influencing. The planarisation is estimated to be incomplete because a full planarisation according to PLICT would cause very strong repulsion of the peri-situated hydrogen atoms. The subsequent fluorescence is bathochromically shifted with respect to light absorption because of the relaxation processes where the solvent influence on the excited state allows a control of the emission maximum and the variation of the Stokes' shift from 1.7 eV in heptane to 5.7 eV in methanol; see Table 1. The photo-induced mechanism in Figure 3 corresponds to the dynamic process described for DPP fluorescent dyes: Scheme 2 in ref.33 The fluorescence quantum yields of 3a and 3b, respectively, are appreciably solventdependent where more than 60% were found in cyclohexane slightly decreasing with higher solvent polarity indicated by the ET(30) values in Table 1 where comparably moderate fluorescence quantum yield were observed in the dipolar aprotic solvents acetonitrile, DMF and DMSO and in methanol; this may be a consequence of partially enabling a competing pathway to TICT states by these highly polarisable solvent stabilising the charge separation in a fast solvent effect during electronic excitation. A more detailed view is obtained comparing the fluorescence quantum yields of 3a and 3b for various solvents; see Figure 4, right correlations. The solvent influence is similar on both chromophores with a slightly higher ACS Paragon Plus Environment

Page 7 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


7 sensitivity of 3b (slope 1.19; squares) except the series of the dipolar aprotic solvents acetonitrile, DMF and DMSO and methanol where 3a exhibits an appreciable higher sensitivity (slope 0.21; triangles); specific solvent effects on the trimethoxyphenyl group of 3b may be therefore responsible. -40

40  (3a) in %

0

80

 (3b) in %

 (3b) in ns

60 5 40

20

0

0 0

5

 (3a) in ns

10

Figure 4. Linear correlations between the fluorescence lifetimes  and fluorescence quantum yields  of 3a and 3b for various solvents (see Table 1). Triangles, right an upper scale: Fluorescence quantum yield in the dipolar aprotic solvents acetonitrile, DMF and DMSO and in methanol (slope 0.21, correlation number 0.993, standard deviation 0.33 for 4 solvents); squares: The other solvents of Table 1 (slope 1.19, correlation number 0.988, standard deviation 2.7 for 8 solvents). Fluorescence lifetimes  with left and lower scales. Circles for monoexponential and 1 of bi-exponential decay. For dipolar protic solvents and methanol: Slope 0.056, correlation number 0.983, standard deviation 0.03 for 4 solvents; (for the other solvents: Slope 1.46, correlation number 0.984, standard deviation 0.1 for 8 solvents) and diamonds for 2 except ethanol (slope 0.76, correlation number 0.999, standard deviation 0.6 for 4 solvents).

The fluorescence lifetime of 3a depends slightly on the applied solvent and varies from typical 4.4 ns in chloroform to 2.8 ns in ethanol (second component with 7.7 ns) and is similar to the fluorescence lifetime of the solid state (2.1 and 6.2 ns). A comparison of the fluorescence lifetimes of 3a and 3b for various solvents exhibits a similar tendency as the ACS Paragon Plus Environment


Page 8 of 17

8 fluorescence quantum yields as is expected according the analyses of Perrin34 and Strickler and Berg35 (for limitations see ref.36,37); see Figure 4, left correlations: A slope of 1.46 indicates a slightly higher sensitivity of 3b for most solvents except the dipolar aprotic solvents acetonitrile, DMF and DMSO and methanol where a bi-exponential fluorescence decay is observed. A low slope of 0.056 is found for the short component 1 indicating an appreciably higher solvent influence on 3a. A more similar influence is observed for the long component 2 with a slope of 0.74. Here, ethanol seems to be an exception due to specific solvent effects because a small, but significant fraction of a very long lasting component was found with 2 = 22 ns for 3b. The mechanism of Figure 3 was further supported by quantum chemical calculations (DFT B3LYP) of the N-methyl derivative of 3a (R = CH3) where an appreciable shift of charge from the methoxynaphthyl subunit to the perylenecarboximide is obtained from a transition of HOMO to LUMO; see Figure 5.

Figure 5. Calculated (DFT B3LYP) orbitals HOMO (lower) and LUMO (upper) of 3a (R = CH3).


Page 9 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


9 Figure 6. Dihedral angles between the methoxynaphthalene and the perylene carboximide substructures calculated of the electronic ground state (left, DFT B3LYP) of 3a (R = CH3) and the electronically excited state (right, CIS).

Moreover, a comparably large dihedral angle of 79° between the methoxynaphthalene and the perylene carboximide substructures was calculated for the electronic ground state of 3a; see Figure 6, left. The dihedral angle is diminished to 65° by optical excitation, however, still remains far away from a complete planarisation according to PLICT where the increased conjugation favours the optical transition of fluorescence indicated by comparably high fluorescence quantum yields.

520 nm

0.8 550 nm

y 0.6

polarity 600 nm

0.4

0.2 480 nm

0 0

0.2

0.4

0.6

x

0.8

Figure 7. Colour coordinates (CIE 1931, 2°) of solutions of 3a in various solvents (see Table 1). Points near by the centre (black point): Colour (D65) of absorption of solutions with 10% light transmission in the maximum. Points at the periphery: Colour of fluorescence (black points: Fundamental wavelengths).

The comparably strong fluorescence of 3a with clear colour prompted us to calculate38 the colour coordinates and preferred CIE 1931 with a small opening angle of 2° because typical optical impressions for direct point-view. There is only a slight solvent influence on the colour of light absorption extending in the region of pale orange according to the weak solvatochromism of light absorption (Figure 7, points near by the centre). On the other hand, ACS Paragon Plus Environment


Page 10 of 17

10 the bright, clear colours of fluorescence close to the spectral pure colours are shifted from yellowish green to red by means of increasing solvent polarity; see points at the periphery in Figure 7. Even a fine-tuning is possible by the application of solvent mixtures. Conclusions Concluding, the attachment of donor-substituted aryl groups to the perylenedicarboximide skeleton in peri-position, preferably 4-methoxynaphthyl, yields highly fluorescent dyes with large Stokes' shifts and solvent-tuneable bright and clear colour in emission. A sequence of dynamic steps create the impression of molecular machines where sterically restricted rotation (SRR) by peri-hydrogen atoms is made responsible for an incomplete PLICT causing both a bathochromic shift and a strong solvatochromism of fluorescence (i-PLICT). The clear colours of fluorescence can be shifted from clear greenish yellow to red and can be thus tuned for applications. Experimental section General Information. Available standard chemicals were applied in synthesis grade without further

purification.

1-Butanol,

chloroform,

hexane

and

toluene

were

used

in

spectrophotometric grade. DMF, tetradecane and 1-undecanol were used in p.a. grade and stored over 3 Å molar sieve. Toluene and THF were continuously refluxed and freshly distilled from sodium benzophenone ketyl under nitrogen and stored over 4 Å molecular sieves. Yields refer to isolated compounds estimated to be > 95 % pure as determined by 1H

NMR (25 °C) and capillary GC. Chemical shifts are reported as -values in ppm relative to

the solvent peak. NMR spectra were recorded in a solution of CDCl3 (residual chloroform:  = 7.27 ppm for 1H NMR and  = 77.0 ppm for

13C{1H}

NMR). Abbreviations for signal

coupling are as follows: s, singlet; br s, broad singlet; d, doublet; t, triplet; q, quartet; quin, quintet; sxt, sextet; m, multiplet. Infrared spectra were recorded from 4000-400 cm-1 on a Perkin 281 IR spectrometer. Samples were measured neat (ATR, Smiths Detection DuraSample IR II Diamond ATR). The absorption bands were reported in wave numbers (cm1).

Mass Spectra were recorded on Finnigan MAT 95Q or Finnigan MAT 90 instrument for

electron impact ionization (EI) with direct vaporization of the sample (DEP/EI) from a platinum fiber 20 until 1600°C at 60°C·min-1. High Resolution Mass Spectra (HRMS) were recorded on the same instrument. UV/Vis spectra were obtained with a Varian Cary 5000 ACS Paragon Plus Environment

Page 11 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


11 spectrometer. Fluorescence spectra were obtained with a Varian Cary Eclipse spectrometer, slit width 2.5 nm. Fluorescence lifetimes  were obtained with a PicoQuant 300lifetime spectrometer and a PicoQuant, P-C-405 as light source. Column chromatography was performed using SiO2 (0.040 – 0.063 mm, 230 – 400 mesh ASTM) from Merck if not indicated. Fluorescence quantum yields were determined analogously to ref.39 The interpretation of NMR signals was verified with carbon-proton (HMBC) and proton-proton (COSY, NOESY) correlation methods. All reagents were obtained from commercial sources and used without further purification if not otherwise stated.

8-(4-Methoxynaphthalen-1-yl)-2-(tridecan-7-yl)-1H-benzo[10,5]anthra[2,1,9def]isoquinoline-1,3(2H)-dione (3a): In a Schlenk flask under a light stream of argon 8bromo-2-(tridecan-7-yl)-1H-benzo[10,5]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (2, 300 mg, 0.52 mmol, 1.0 equiv.) and 2-(4-methoxynaphthalen-1-yl)-4,4,5,5-tetramethyl-1,3,2dioxaborolane (156 mg, 0.55 mmol, 1.05 equiv.) were dissolved in toluene (10 mL), treated with K2CO3 (1.40 g, 10.0 mmol) dissolved in a mixture of water (5 mL) and ethanol (1 mL) followed by tetrakis(triphenyl-phosphine)palladium(0) (30 mg, 0.026 mmol, 5 mol%), purged with argon for 30 min and then heated to 80 °C (oil bath), stirred at this temperature for further 17 h, allowed to cool to room temperature, collected and extracted with toluene (3x10 mL) and purified by column separation (silica gel, CHCl3): Yield 310 mg (91%) red solid, m.p. 161-163 °C. IR (diamond-ATR, neat):

= 2924, 2855, 1689, 1651, 1587, 1575, 1510,

1462, 1350, 1294, 1238, 1092, 807, 767, 750 cm-1. 1H NMR (600 MHz, CDCl3): δ = 8.678.56 (br, 2H), 8.54 (d, J = 7.9 Hz, 1H), 8.48 (d, J = 8.2 Hz, 1H), 8.44 (d, J = 8.1 Hz, 2H), 8.41 (d, J = 9.1 Hz, 1H), 7.65 (d, J = 7.6 Hz, 1H), 7.55 (dd, J = 8.4, 1.0 Hz, 1H), 7.52-7.48 (m, 1H), 7.47-7.42 (m, 2H), 7.42-7.39 (m, 1H), 7.38-7.34 (m, 1H), 6.98 (d, J = 7.9 Hz, 1H), 5.255.19 (m, 1H), 4.12 (s, 3H), 2.31-2.22 (m, 2H), 1.91-1.83 (m, 2H), 1.40-1.21 (m, 16H), 0.83 (t, J = 7.0 Hz, 6H) ppm.

13C{1H}

NMR (150 MHz, CDCl3):  = 165.4, 164.4, 155.8, 142.0,

137.3, 134.4, 133.6, 132.2, 131.4, 130.2, 129.9, 129.7, 129.8, 129.7, 129.5, 128.9, 128.3, 128.1, 127.0, 126.8, 126.2, 125.7, 125.5, 123.8, 123.5, 122.5, 120.4, 120.2, 103.5, 55.8, 54.6, ACS Paragon Plus Environment


Page 12 of 17

12 32.6, 32.0, 29.4, 27.1, 22.8, 14.2 ppm. MS (DEP/EI, 70 eV): m/z (%) = 660 (50), 659 (100), 478 (70), 477 (98), 463 (19), 462 (16), 446 (12), 445 (14), 69 (11), 55 (15), 44 (24). HRMS (DEP/EI) m/z: M+ Calcd. for C46H45NO3: 659.3399; Found: 659.3393. 2-(Tridecan-7-yl)-8-(3,4,5-trimethoxyphenyl)-1H-benzo[10,5]anthra[2,1,9def]isoquinoline-1,3(2H)-dione (3b): In a Schlenk-flask under a light stream of argon 8bromo-2-(tridecan-7-yl)-1H-benzo[10,5]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (2, 300 mg, 0.52 mmol, 1.0 equiv.) and 3,4,5-trimethoxyphenylboronic acid (117 mg, 0.55 mmol, 1.05 equiv.) were dissolved in toluene (10 mL), treated with K2CO3 (1.40 g, 10.0 mmol) dissolved in a mixture of water (5 mL) and ethanol (1 mL) followed by tetrakis(triphenylphosphine)palladium(0) (30 mg, 0.026 mmol, 5 mol%), purged with argon for 30 min and then heated to 80 °C (oil bath), stirred at this temperature for further 17 h, allowed to cool to room temperature, collected and extracted with toluene (3x10 mL) and purified by column separation (silica gel, CHCl3). Yield 325 mg (94%), red solid, m.p. 146148 °C. IR (diamond-ATR, neat):

= 2922, 2853, 1684, 1646, 1589, 1570, 1499, 1462, 1401,

1350, 1289, 1242, 1124, 1007, 836, 807, 751 cm-1. 1H NMR (600 MHz, CDCl3):  = 8.638.54 (m, 2H), 8.46 (dd, J = 7.5, 2.6 Hz, 2H), 8.44-8.41 (m, 2H), 8.04 (d, J = 8.3 Hz, 1H), 7.62-7.59 (m, 1H), 7.59 (d, J = 7.7 Hz, 1H), 6.74 (s, 2H), 5.22-5.17 (m, 1H), 3.98 (s, 3H), 3.92 (s, 6H), 2.29-2.23 (m, 2H), 1.90-1.83 (m, 2H), 1.37-1.20 (m, 16H), 0.83 (t, J = 7.1 Hz, 6H) ppm.

13C{1H}

NMR (150 MHz, CDCl3):  = 165.3, 164.3, 153.4, 143.3, 137.9, 135.6,

132.9, 132.1, 131.3, 130.1, 129.6, 129.4, 128.8, 128.5, 128.1, 127.2, 126.7, 123.8, 123.3, 120.5, 120.2, 107.4, 61.2, 56.5, 54.6, 32.6, 31.9, 29.4, 27.1, 22.8, 14.2 ppm. MS (DEP/EI, 70 eV): m/z (%) = 670 (46), 669 (100), 652 (10), 489 (13), 488 (48), 487 (92). HRMS (DEP/EI) m/z: M+ Calcd. for C44H47NO5: 669.3454; Found: 669.3437. C44H47NO5 (669.9): Calcd. C 78.79, H 7.07, N 2.09; Found C 78.73, H 6.99, N 2.19.


Page 13 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


13 ASSOCIATED CONTENT Supporting Information: NMR spectra, quantum chemical calculations and TCSPC measurements of 3a and 3b are available free of charge via the Internet at http://pubs.acs.org AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. com. Tel: +49-89-2180-77699. ORCID Heinz Langhals: 0000-0002-8038-4547, Robert Greiner: 0000-0002-0262-5990, Thorben Schlücker: 0000-0002-6419-7944, Andreas C. Jakowetz 0000-0001-7804-7210. Author Contributions All of the authors contributed to the work in order to complete the work and all authors played a role in writing the manuscript. Notes The authors declare no competing financial interest. Acknowledgment. Financial support by the Fonds der Chemischen Industrie and the CIPSM cluster Munich Center for Integrated Protein Science is gratefully acknowledged.

References (1) Jameson, D. M. (ed.) Introduction to Fluorescence. CRC Press, Boca Raton, Fla. 2014; ISBN:978-1-4398-0604-3. (2) Watanabe S. (ed.) Fluorophores: Characterization, Synthesis And Applications. Nova Science Publishers, Inc., Hauppauge, N. Y. 2013, SBN:978-1-62808-268-5. (3) Valeur, B.; Berberan-Santos, M. N. Molecular Fluorescence, Second Edition. Wiley, Hoboken, N. J. 2012; ISBN:978-3-527-32837-6.



Page 14 of 17

14 (4) Geddes, C. D. (ed.) Reviews in Fluorescence 2009. [In: Rev. Fluoresc. 2011; 6], 2011 DOI:10.1007/978-1-4419-9672-5; ISBN:978-1-4419-9671-8; Chem. Abstr. 2011, 156, 406162. (5) Gladysz, J. A.; Curran, D. P.; Horvath, I. T. (eds.) Handbook of Flurorous Chemistry. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany 2004; ISBN:3-527-30617-X. (6) Langhals, H. Chromophores for picoscale optical computers in Sattler, K. (ed.), Fundamentals of picoscience. P. 705-727, Taylor & Francis Inc. CRC Press Inc., Bosa Roca/US 2013; ISBN 13: 9781466505094, ISBN 10: 1466505095. (7) Langhals, H. Control of the Interactions in Multichromophores: Novel Concepts. Perylene Bisimides as Components for Larger Functional Units. Helv. Chim. Acta 2005, 88, 13091343. (8) Langhals, H. Cyclic Carboxylic Imide Structures as Structure Elements of High Stability. Novel Developments in Perylene Dye Chemistry. Heterocycles 1995, 40, 477-500. (9) Duarte, F. J. (ed.) Springer Series in Optical Sciences, Vol. 65: High-Power Dye Lasers. Springer, Berlin (Germany) 1991. (10) Maeda, M. Laser Dyes: Properties of Organic Compounds for Dye Lasers. Academic Press, Inc., Tokyo, Japan 1984. (11) Schaefer, F. P. (ed.), Topics in Applied Physics, Vol. 1: Dye Lasers. 2nd Rev. Ed.. Springer-Verlag, Berlin (Germany) 1977. (12) Slooff, L. H.; Bakker, N. J.; Sommeling, P. M.; Buechtemann, A.; Wedel, A.; van Sark, W. G. J. H. M. Long-term Optical Stability of Fluorescent Solar Concentrator Plates. Physica Status Solidi A: Applications and Materials Science 2014, 211, 1150-1154. (13) Swift, P. D.; Smith, G. B. Color Considerations in Fluorescent Solar Concentrator Stacks. Applied optics 2003, 42, 5112-5117.


Page 15 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


15 (14) Mugnier, J.; Dordet, Y.; Pouget, J.; Le Bris, M. T.; Valeur, B. Performances of Fluorescent Solar Concentrators Doped with a New Dye (Benzoxazinone Derivative). Solar Energy Materials 1987, 15, 65-75; Chem. Abstr. 1987, 106, 105406. (15) Goetzberger, A.; Greubel, W. Solar Energy Conversion with Fluorescent Collectors. Appl. Phys. 1977, 14, 123-139. (16) Langhals, H. Dyes for Fluorescent Solar Collectors. Nachr. Chem. Tech. Lab. 1980, 28, 716-718; Chem. Abstr. 1981, 95, R9816q. (17) Garvin, R. L. The Collection of Light from Scintillation Counters. Rev. Sci. Instr. 1960, 31, 1010-1011. (18) Valeur, B.; Brochon, J.-C. (eds.) New Trends in Fluorescence Spectroscopy: Applications to Chemical and Life Sciences. Springer Verlag, Heidelberg 2001; ISBN 978-3642-63214-3. (19) Langhals, H.; v. Unold, P. Tetracarboxylic Bisimide-lactame-ring-contractions: A Novel Type of Rearrangement. Angew. Chem. 1995, 107, 2436-2439; Angew. Chem., Int. Ed. 1995, 34, 2234-2236. (20) Turro, N. J. Modern Molecular Photochemistry, University Science Books, Sausalito (CA) 1991; ISBN 978-0-935702-7-12. (21) Lewis, G. N.; Calvin, M. The Color of Organic Substances. Chem. Rev. 1939, 25, 273328. (22) Langhals, H.; Hofer, A. Controlling UV/Vis Absorption and Stokes' Shifts in Highly Fluorescent Chromophores by Molecular Dynamics in Targeted Construction of Dyads. J. Org. Chem. 2012, 77, 9585-9592. (23) Greiner, R.; Schlücker, T.; Zgela, D.; Langhals, H. Fluorescent Aryl Naphthalene Carboximides with Large Stokes' Shifts and Strong Solvatochromism Controlled by Dynamics and Molecular Geometry. J. Mater. Chem. C 2016, 4, 11244-11252.



Page 16 of 17

16 (24) Haberhauer, G.; Gleiter, R.; Burkhart, C. Planarized Intramolecular Charge Transfer: A Concept for Fluorophores with both Large Stokes Shifts and High Fluorescence Quantum Yields. Chem. Eur. J. 2016, 22, 971-978. (25) Zhong, C. The Driving Forces for Twisted or Planar Intramolecular Charge Transfer. Phys. Chem. Chem. Phys. 2015, 17, 9248-9257. (26) Grabowski, Z. R.; Rotkiewicz, K.; Rettig, W. Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures. Chem. Rev. 2003, 103, 3899-4032. (27) Rettig, W. Charge Separation in Excited States of Decoupled Systems: Twisted Intramolecular Charge Transfer (TICT) Compounds and Implications for the Development of New Laser Dyes and for the Primary Process of Vision and Photosynthesis. Angew. Chem. 1986, 98, 969-986; Angew. Chem. Int. Ed. 1986, 25, 971-988. (28) Feiler, L.; Langhals, H.; Polborn, K. Synthesis of Perylene-3,4-dicarboximides - Novel, Highly Photostable Fluorescent Dyes. Liebigs Ann. Chem. 1995, 1229-1244. (29) Dimroth, K.; Reichardt, C.; Siepmann, T.; Bohlmann, F. Pyridinium N-Phenolbetaines and their Use for the Characterization of the Polarity of Solvents. Justus Liebigs Ann. Chem. 1963, 661, 1-37. (30) Reichardt, C. Empirical parameters of solvent polarity. Angew. Chem. 1965, 77, 30-40; Angew. Chem., Int. Ed. 1965, 4, 29-40. (31) Machado, V. G.; Stock, R. I.; Reichardt, C. Pyridinium N-Phenolate Betaine Dyes. Chem. Rev. 2014, 114, 10429–10475. (32) Langhals, H. Heterocyclic Structures Applied as Efficient Molecular Probes for the Investigation of Chemically Important Interactions in the Liquid Phase. Chem. Heterocycl. Compd. 2017, 53, 2-10; DOI: 10.1007/s10593-017-2014-z. (33) Potrawa, T.; Langhals, H. Fluorescent Dyes with Large Stokes' Shifts: Soluble Dihydropyrrolopyrroldiones. Chem. Ber. 1987, 120, 1075-1078. ACS Paragon Plus Environment

Page 17 of 17 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


17 (34) Perrin F. Polarisation de la lumière de fluorescence: Vie moyenne des molécules dans l’état excité. J. Phys. Radium Serie 6 1926, 7, 390–401. (35) Strickler, S. J.; Berg, R. A. Relationship between Absorption Intensity and Fluorescence Lifetime of Molecules. J. Chem. Phys. 1962, 37, 814-822. (36) Ware, W. R.; Baldwin, W. A. Absorption Intensity and Fluorescence Lifetimes of Molecules. J. Chem. Phys. 1964, 40, 1703-1705. (37) Langhals, H. From the General to the Individual Case: Concepts on the Test Bench. Nachr. Chem. Tech. Lab. 2018, 66, 601-604; DOI:10.1002/nadc.20184072731; Chem. Abstr. 2018, AN1086710. (38) Osram ColorCalculator; Osram Sylvania Inc.; https://www.osram.us/cb/tools-andresources/applications/led-colorcalculator/index.jsp (5-3-2019). (39) Langhals, H.; Karolin, J.; Johansson, L. B.-Å. Spectroscopic Properties of New and Convenient Standards for Measuring Fluorescence Quantum Yields. J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922.


Light-Driven Molecular Dynamics in Perylenes with Medium

Recommend Documents