ES2951005A1 - SYNTHESIS OF HELICAL CARBAZOLES THAT PRESENT AN IMIDAZOLE RING (Machine-translation by Google Translate, not legally binding) - Google Patents

Abstract

Synthesis of helical carbazoles that have an imidazole ring. The present invention relates to the compounds of general formula (I) and (II) and their method of preparation. Compounds (I) and (II) are polycyclic aromatic helicenes that have an imidazole ring in their structure. Helicenes are aromatic polycycles containing aromatic rings fused in an angular arrangement that exhibit enhanced chiroptical properties due to their deviation from planarity. Furthermore, the invention refers to the possible uses of said compounds in the preparation of dyes, in particular deep blue luminescent emitters for application in biological detection, in organic lasers and in fluorescent probes. (Machine-translation by Google Translate, not legally binding)

Description

DESCRIPTION

SYNTHESIS OF HELICAL CARBAZOLES THAT PRESENT AN IMIDAZOLE RING

TECHNIQUE SECTOR

The present invention falls within the sector of the synthesis of organic compounds. More specifically, it refers to a procedure for the synthesis of helical carbazoles that have an imidazole ring that are useful in the production of dyes. In particular, they are deep blue luminescent emitting compounds for application in biological detection, in organic lasers and in fluorescent probes.

BACKGROUND OF THE INVENTION

Dyes and pigments attract considerable attention due to their use in biological and material applications. A particularly relevant class of dyes are deep blue luminescent emitters (Scheme 1), with applications ranging from biological sensing to organic lasers (C. He, H. Guo, Q. Peng, S. Dong and F. Li, J. Mater. Chem. C, 2015, 3, 9942-9947; SS Reddy, VG Sree, W. Cho and SH Jin, Chem. Asian J., 2016, 11, 3275-3282; WC Chen, Y. Yuan, SF Ni, ZL Zhu, J. Zhang, ZQ Jiang, LS Liao, FL Wong and CS Lee, ACS Appl. Mater. Interfaces, 2017, 9, 7331-7338; J.-H. Lee, C.-H. Chen, P.-H. Lee, H.-Y. Lin, M. Leung, T. -L. Chiu and C.-F. Lin, J. Mater. Chem. C, 2019, 7, 5874-5888 ; H. Min, IS Park and T. Yasuda, Angew. Chem. Int. Ed., 2021, 60, 7643-7648).

Several cyclic compounds incorporating an imidazole ring have demonstrated good electronic and emitting properties in this blue region of light (WC Chen, Y. Yuan, SF Ni, QX Tong, FL Wong and CS Lee, Chem. Sci., 2017, 8, 3599-3608; W.-C.

Chen, Z.-L. Zhu and C.-S. Lee, Adv. Opt. Mater., 2018, 6, 1800258; ER Sauvé, CM Tonge and ZM Hudson, J. Mater. Chem. C, 2021, 9, 4164-4172).

On the other hand, the carbazole nucleus is a fundamental type of heterocycle due to the widespread presence of this ring in bioactive compounds, advanced materials and natural products (T.-Y. Shang, L.-H. Lu, Z. Cao, Y. Liu, W.-M. He, B. Yu, Chem. Commun. 2019, 55, 5408-5419; M. L¡, Chem. Eur. J. 2019, 25, 1142-1151; AW Schmidt, KR Reddy, H.-J. Knólker, Chem. Rev. 2012, 112, 3193-3328; HJ Jiang, J. Sun, JL Zhang, Curr. Org. Chem. 2012, 16, 2014-2025; J. Roy, AK Jana, D. Mal, Tetrahedron 2012, 68, 6099-6121; J. Li, AG Grimsdale, Chem. Soc. Rev. 2010, 39, 2399-2410).

Furthermore, helicenes are aromatic polycycles containing aromatic rings fused in an angular arrangement that show improved chiroptical properties due to their deviation from planarity (A. Urbano and MC Carreño, Org. Biomol. Chem., 2013, 11, 699-708 ; M. Gingras, G. Félix and R. Peresutti, Chem. Soc. Rev., 2013, 42, 1007-1050; T. Mori, Chem. Rev., 2021, 121, 2373-2412).

Consequently, the development of an efficient protocol for the synthesis of compounds that incorporate the three previous structures, carbazole helicene and imidazole, is highly desirable for the search for blue emitters and heterocycles with pharmacological properties.

EXPLANATION OF THE INVENTION

In the present invention, imidazoles fused to carbazolic azahelicenes are described, as well as their synthesis method from easily available 3-iodo-2-formyl indoles. The compounds obtained can be used as deep blue luminescent emitting compounds.

Therefore, a first aspect of the invention refers to the compounds of general formula (I) and (II) (hereinafter compounds of the invention) where:

R1 and R2 are the same or different from each other and are selected from the list comprising hydrogen (H), an alkyl group (Ci-Cs) an aryl group (C6-Cis) or alkoxyl (ORa).

R3 and R4 are the same or different from each other and are selected from the list comprising hydrogen (H), an alkyl group (Ci-Cs) or an aryl group (C6-Cis).

R5 is selected from the list comprising hydrogen (H), an alkyl group (Ci-Cs) an aryl group (C6-Cis) or a fused aromatic.

The term "alkoxyl" refers herein to a group of formula -ORa in which Ra is an alkyl (Ci-Cs), such as, for example, and not limited to, methoxy, ethoxy, propoxy or benzyloxy. Preferably the alkoxyl is a methoxyl.

The term "alkyl" refers in the present invention in the case of R1 and/or R2 and/or R3 to aliphatic chains, linear or branched, having from 1 to 8 carbon atoms; for example, methyl, ethyl, n-propyl, /-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n- hexyl, although preferably they have 1 to 3 carbon atoms. The alkyl groups may be optionally substituted by one or more substituents such as nitro, hydroxyl, azide, halogen, carboxylic acid or by a group, substituted or unsubstituted, selected from: aryl, hydroxyl, amido, amino, ester, carboxylic acid , ether, thiol, acylamino, carboxamido or nitro. When the alkyl group is substituted by an aryl it is described as "arylalkyl", as, for example, but not limited to, in the case of a benzyl group.

The term "aryl" refers in the present invention to an aromatic carbocyclic chain, which has from 6 to 18 carbon atoms, and can be a single or multiple ring, in the latter case with separate and/or fused rings. The aryl groups may be optionally substituted by one or more substituents such as alkyl, alkoxy, nitro, hydroxyl, azide, halogen, or carboxylic acid. As examples of an aryl group, and not limited to, the groups; phenyl, naphthyl, indenyl or anthranyl. Preferably the aryl group is a phenyl.

The term "cycloalkyl" refers herein to a 3- to 12-membered monocyclic or polycyclic aliphatic chain, which is saturated or partially saturated, and consisting only of carbon and hydrogen atoms, such as cyclopropyl, cyclohexyl or norbornyl.

The term "heterocycle" refers herein to a monocyclic or polycyclic chain of 3 to 12 members, which is saturated, partially saturated or unsaturated, and which consists of carbon atoms and at least one heteroatom selected from the group consisting in nitrogen, oxygen, sulfur or selenium. Preferably the heteroatom is nitrogen and the cycle is a ring of 5 or 6 members. Examples of heterocycles may be mentioned, but are not limited to: pyrrole, pyrrolidine, piperidine and indole.

In another preferred embodiment of the compounds of the invention, R2, and R5 are alkyl groups (Ci-Cs). More preferably R2 is hydrogen and/or alkyl and R5 are alkyl groups. More preferably R5 are benzyl groups.

In another preferred embodiment of the compounds of the invention, R2, R5 are alkyl (Ci-Cs) or aryl (C6-Cis) groups. More preferably R2 is alkyl and/or R5 are aryl groups. More preferably R2 is methyl, R5 are substituted phenyl groups.

In another preferred embodiment of the compounds of the invention, R2 is hydrogen, R5 are aryl groups (C6-Cis). More preferably R5 are substituted phenyl groups.

In a more preferred embodiment, the compounds of the invention are selected from compounds 1 to 4, of general formula (I), and compounds 5 to 8, of general formula (II):

The compounds of the present invention represented by formula (I) may include isomers, depending on the presence of multiple bonds (for example Z, E), including optical isomers or enantiomers, depending on the presence of centers chiral. Individual isomers, enantiomers or diastereomers or mixtures thereof fall within the scope of the present invention, that is, the term isomer also refers to any mixture of isomers, such as diastereomers, racemic, etc., including their optically isomers. active ingredients or mixtures in different proportions thereof. The individual enantiomers or diastereomers, as well as their mixtures, can be separated by conventional techniques.

The compounds of the present invention of formula (I) can be obtained or produced by chemical synthesis or generated from a natural material of different origin.

Another aspect of the present invention refers to a procedure for obtaining the compounds of the invention of formula (I) or an isomer, its salts and/or solvate thereof, which comprises the following steps summarized in Scheme 3:

A) Preparation of carbazoles [general formula (III) and (IV)] by reaction of the indolic terminal alkyne with 3-iodo-2-formyl indoles.

B) Preparation of helical carbazoles (I) and (II) by the reaction of iodocarbazoles of general formula (III) and (IV) in the presence of 1,2-diamines and copper catalysis.

Previously, the metal-catalyzed synthesis of iodocarbazoles (stage A) from an indolic butynol has been described (Alcaide, B. et al. ACS Catal., 2015, 5, 3417 3421; Martín-Mejías, I. et al. Adv. Synth, Catal., 2021, 363, 1449-1456). Under conventional Sonogashira conditions, the reaction does not stop at non-terminal alkynes and evolves to chromatographically separable iodocarbazoles. It was found that treatment of these fused and functionalized tricycles with a copper-catalyzed formyl indole moiety in the presence of 1,2-diamines leads to the formation of helical carbazoles featuring an imidazole ring (step B).

A third aspect of the invention refers to the compounds of general formula (I) and (II) for their use in the preparation of dyes, in particular deep blue luminescent emitters for their application in biological detection, in organic lasers and fluorescent probes.

The term “luminescence” refers to the process of light emission.

The term “luminescent emitter” as used herein refers to a compound that transforms energy into a luminescent signal.

Another aspect of the invention refers to a deep blue luminescent emitting dye comprising one or more compounds of general formula (I) or one or more compounds of general formula (II). In a preferred embodiment the dye comprises one or more compounds of formulas 1 to 11 as well as individual enantiomers or diastereomers of the compounds of formulas 1 to 11 or mixtures thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, a set of figures is attached as part of said description where, with an illustrative and non-limiting nature, the following is represented. :

Figure 1. Absorption and emission spectra of compounds 5, 9, 10 and 11.

Figure 2. Photophysical properties of compound 9 in different media: dichloromethane (DCM), methanol (MeOH) and heptane (Hept).

Figure 3. Photophysical properties of compound 5 in different media: dichloromethane (DCM), methanol (MeOH) and heptane (Hept).

PREFERRED EMBODIMENT OF THE INVENTION

Next, the invention will be illustrated through tests carried out by the inventors, which are not, however, limiting the scope of the invention.

Example 1

This example refers to the method of preparing helical helicenes of general formula (I) and (II) from carbazoles (III) and (IV), respectively.

To a solution of carbazole (20 mg, 0.043 mmol) in AcOH/DMF (1:1) (0.52 mL), ortho-amino aniline (4.8 mg, 0.043 mmol) and a metal catalyst (0.043 mmol) are added. .0043 mmol). The reaction mixture is then heated at 100°C in the microwave for 3 hours (TLC). The resulting residue is extracted with AcOEt (3 x 10 mL) and the organic phase is washed with H20 (3 x 10 mL), dried over MgSÜ4. The crude oil is purified by column chromatography with silica gel.

Example 2

This example refers to the method of preparation of 5,18-Dimethyl-5,18-dihydrobenzo[4',5']imidazo[1',2':1,6]indolo[3',2':4,5 ]pyrido[3,2-a]carbazole (compound 9).

From 3-(2-iodo-9-methyl-9H-carbazol-1-yl)-1-methyl-1H-indole-2-carbaldehyde (40 mg, 0.086 mol), 24 mg (0.056 mmol, 65%) of the final product after purification using a silica gel chromatography column, using a mixture of n-hexane/AcOEt (3:1) as eluent.

The compound obtained is a whitish yellow solid. In solution and in contact with UV radiation, fluorescence emission of a bluish color is observed. Since it is a solid, the melting point was measured. Before melting, the molecule was observed to decompose. The temperature range was 225°C - 227°C.

1H NMR (700 MHz, CDCl ₃ ): ó = 8.59 (2H, dd, J = 8.40, 3.30 Hz, HAr), 8.55 (1H, d, J = 8.12 Hz, HAr), 8.26 (1H, d, J = 8.33 Hz, HAr), 8.22 (1H, d, J =7.58 Hz, HAr), 8.14 (1H, d, J = 7.50 Hz, HAr), 7.68 (1H, d, J =8.01 Hz, HAr), 7.65 ( 1H, d, J = 8.14 Hz, HAr), 7.61 (2H, dt, J = 10.24, 7.50 Hz, HAr), 7.55 (2H, q, J = 6.83Hz, HAr), 7.40 (2H, dt, J = 60.35, 7.49 Hz, HAr), 4.76 (3H, s, N-CH ₃ ), 3.79 (3H, s, N-CH ₃ ): 13C NMR (175 MHz, CDCl ₃ ): or = 146.3 (CAr), 144.8 (CAr), 142.2 (CAr), 140.8 (CAr), 140.5 (CAr), 132.3 (CAr), 131.4 (CAr), 126.0 (CHAr), 125.2 (CAr), 125.1 (CHAr), 125.0 (CAr), 124.3 (CHAr), 124.27 (CAr), 124.2 (CAr)123.7 (CHAr), 122.7 (CHAr), 122.6 (CAr), 121.1 (CHAr), 120.3 (CHAr), 120.2 (CHArx2), 117.8 (CHAr), 113.9 ( CHAr), 111.7 (CHAr), 110.1 (CHAr), 109.3 (CHAr), 108.5 (CAr), 37.2(CH ₃ ), 29.7 (CH ₃ ); HRMS (ES): caled for C29H20N4 [M+H]+: 425.1733; found: 425.1761.

Example 3

This example refers to the method of preparation of 9,18-Dimethyl-9,18-dihydrobenzo[4',5']imidazo[1',2':1,6]indolo[3',2':4,5 ]pyrido[2,3-c]carbazole (compound 5).

From 3-(3-iodo-9-methyl-9H-carbazol-4-yl)-1-methyl-1H-indole-2-carbaldehyde (16 mg, 0.034 mmol), 12 mg (0.028 mmol, 80%) of the final product, after purification using a silica gel chromatography column, using a mixture of n-hexane/AcOEt (3:1) as eluent. The compound obtained is a whitish yellow solid. In this isomer, fluorescence is also observed in solution upon contact with UV radiation. The observed color has a more violet tone than the previous compound.

Since it is a solid, the melting point is measured. Before melting, the molecule is observed to decompose. The temperature range was 229°C - 231°C.

1H NMR (700 MHz, CDCl ₃ ): 5 = 8.84 (1H, d, J = 8.99 Hz, HAr), 8.56 (1H, dd, J = 7.57, 1.45 Hz, HAr), 8.11 (1H, m, HAr) , 7.98 (1H, m, HAr), 7.85 (1H, d, J = 8.25 Hz, HAr), 7.69 (2H, m, HAr), 7.54 (5H, m, HAr), 7.18 (2H, m, HAr) , 4.80 (3H, s, N-CH ₃ ), 4.07 (3H, s, N-CH ₃ ); 13C NMR (175 MHz, CDCl ₃ ): 5 = 144.8 (CAr), 142.0 (CAr), 141.3 (CAr), 140.8 (CAr), 138.9 (C _Ar ), 131.4 (C _Ar ), 127.6 (CAr), 127.1 (CAr), 126.2 (CHAr), 125.9 (CHAr), 125.4 (CHAr), 124.7 (CHAr), 123.9 (CHAr), 123.5 (CAr), 123.4 (CAr), 122.3 (CHAr), 120.3 (CHAr), 119.2 (CHAr), 117.7 (CHAr), 117.1 (CAr), 115.7 (CAr), 113.9 (CAr), 113.8(CHArx2), 109.7 (CHAr), 108.3 (CHAr), 106.5 (CHAr), 32.3 (CH ₃ ), 29.5 (CH ₃ ). HRMS (ES): caled for C29H20N4 [M+H]+: 425.1761; found: 425.1753.

Example 4

This example refers to the method of preparation of 3-Methoxy-5,18-dimethyl-5,18-dihydrobenzo[4',5']imidazo[1',2':1,6]indolo[3',2' :4,5]pyrido[3,2-a]carbazole (compound 10).

From 3-(2-iodo-9-methyl-9H-carbazol-1-yl)-6-methoxy-1-methyl-1-indole-2-carbaldehyde (23 mg, 0.046 mmol), 11 mg (0.024 mmol, 52%) of the product are obtained, after purification using a silica gel chromatography column using a mixture of n-hexane/AcOEt (2:1) as eluent. The compound obtained is a whitish-yellow solid, which decomposes before melting.

1H NMR (700 MHz, CDCl ₃ ): 5 = 8.59 (1H, d, J= 8.4 Hz, HAr), 8.57 (1H, d, J = 8.2 Hz, HAr) 8.23 (1H, d, J = 8.4 Hz, HAr), 8.21 (1H, d, J = 7.4 Hz, HAr), 8.10 (1H, dd, J = 8.0, 1.2 Hz, HAr), 8.07 (1H, d, J = 2.4 Hz, HAr), 7.63 (1H , d, J = 7.9 Hz, HAr), 7.58 (2H, m, HAr), 7.42 (1H, t, J = 7.3 Hz, HAr), 7.19 (2H, dd, J = 8.8, 2.5 Hz, HAr), 4.72 (3H, s, OCH ₃ ), 3.92 (3H, s, NCH ₃ ), 3.77 (3H, s, NCH ₃ ); 13C NMR (175 MHz, CDCl ₃ ): 5 = 154.2 (CAr), 146.8 (CAr), 144.8 (CAr), 142.3 (CAr), 140.9 (CAr), 135.8 (CAr), 132.2 (CAr), 131.5 (CAr ), 126.4 (CAr), 126.0 (CHAr), 125.4 (CAr), 124.4 (CAr), 124.1 (CHAr), 122.8 (CAr), 122.6 (CHAr), 121.2 (CHAr), 120.2 (CHArx 2), 117.5 ( CHAr), 115.6 (CHAr), 113.9 (CHAr), 112.2 (CAr), 111.6 (CHAr), 110.8 (CHAr), 109.5 (CHAr), 108.8 (CAr), 105.1 (CHAr), 55.8 (CH ₃ ), 37.3 (CH ₃ ), 32.3 (CH ₃ ). HRMS (ES): caled for C30H22N4O [M+H]+: 455.1866; found: 455.1864.

Example 5

This example refers to the method of preparation of 15-Methoxy-9,18-dimethyl-9,18-dihydrobenzo[4',5']imidazo[1',2':1,6]indolo[3',2' :4,5]pyrido[2,3-c]carbazole (compound 11).

From 3-(3-iodo-9-methyl-9H-carbazol-4-yl)-5-methoxy-1-methyl-1H-indole-2-carbaldehyde (9 mg, 0.018 mmol), purifying by column of silica gel chromatography using a mixture of n-hexane/AcOEt (2:1) as eluent, 3 mg (0.007 mmol, 39%) of the final product were obtained.

The compound obtained is a whitish-yellow solid, which decomposes before melting.

1H NMR (700 MHz, CDCl ₃ ): ó = 8.83 (1H, d, J = 8.6 Hz, HAr), 8.55 (1H, d, J = 8.3 Hz,

HAr), 8.13 (1H, d, J = 7.9 Hz, HAr), 7.97 (1H, d, J = 7.8 Hz, HAr), 7.68 (1H, d, J = 8.7

Hz, HAr), 7.58-7.50 (5H, m, HAr), 7.24-7.18 (3H, m, HAr), 4.76 (3H, s, OCH ₃ ), 4.07 (3H,

s, CH ₃ ), 3.54 (3H, s, CH ₃ ); 13C NMR (175 MHz, CDCl ₃ ): ó = 153.3 (CAr), 144.3 (CAr),

141.7 (CAr), 141.6 (C _Ar ), 141.3 (CAr), 138.9 (CAr), 135.9 (CAr), 131.3 (CAr), 127.5 (CAr),

126.8 (CAr), 126.6 (CHAr), 125.4 (CHAr), 123.9 (CHAr), 123.5 (CAr), 123.3 (CAr), 122.4 (CHAr), 120.1 (CHAr), 117.6 (CHAr), 116.7 (CAr), 115.9 (CHAr), 115.8 (CAr), 113.8 (CHAr),

113.7 (CHAr), 110.6 (CHAr), 108.2 (CHAr), 107.3 (CHAr), 106.2 (CHAr), 55.3 (CH ₃ ), 32.5

(CH ₃ ), 29.5 (CH ₃ ); HRMS (ES): caled fo rC 30H22N4O [M+H]+: 455.1866; found: 455.1869.

Example 6

This example shows the photophysical properties of compounds 5, 9, 10 and

11, obtained according to the present invention.

Table 1 shows the photophysical properties determined for compounds 5, 9, 10 and 11 in different solvents. Initially, the medium chosen is dichloromethane because this solvent is where the compounds dissolve best.

The fluorescence lifetime (<x>) is measured by TCSPC ( Time-Correlated Single-Photon Counting) using a 372 nm picosecond laser at 1 MHz repetition rate as excitation effluent. The fluorescence decay time in dichloromethane (DMC) fits a biexponential while in ethanol (MeOH) and heptane (Hept) it fits a monoexponential. In all cases the average life time is calculated by the equation:

where A is the amplitude of each lifetime x.

The fluorescence quantum yield (^fl) is calculated at an excitation wavelength of 368 nm using 9-10-diphenyltanthracene as a reference (^fi (cyclohexane) = 0.9).

The fluorescence radiative constant ^{(K r)} is calculated by the equation:

The two helical carbazoles that present an imidazole ring with all their hydrogen substituents (compounds 5 and 9) present a very similar absorption profile, but with a slight bathochromic shift ( ca. 26 nm) of compound 5 with respect to compound 9 and presenting a very similar absorptivity in both cases (Figure 1). The presence of the methoxide activating group as R2 substituent (compounds 10 and 11) causes the absorptivity to increase with respect to the absorptivity of its peers and, only in the case of compound 11, a slight hypsochromic shift is observed ( ca. 6 nm ) of their absorption peaks.

With respect to their emissive properties, the emission spectra of compounds 9 and 10 present two undifferentiated bands with a maximum located at 415 and 426 nm, respectively, and high fluorescence quantum yields (^n) (0.58 and 0 .44, respectively). Meanwhile, compounds 5 and 11 present an emission profile more defined, with two bands and a shoulder (ca. 430, 456 and 486 for compound 5) and with very similar quantum yields (0.38 and 0.36, respectively), as seen in Figure 1.

When carrying out the tests with other solvents, such as methanol (protic polar solvent) and heptane (apolar solvent), it is concluded, as can be seen in Figures 2 and 3, that the nature of the solvent does not greatly affect the photophysical properties. of the compounds.

Claims (10)

1. Compounds derived from imidazoles fused with carbazolic azahelicenes of general formula (I) and (II).

where: R1 and R2 are the same or different from each other and are selected from the list comprising hydrogen (H), an alkyl group (Ci-Cs) an aryl group (C6-Cis) or alkoxyl (ORa), R3 and R4 are the same or different from each other and are selected from the list comprising hydrogen (H), an alkyl group (Ci-Cs) or an aryl group (C6-Cis), R5 is selected from the list comprising hydrogen ( H), an alkyl group (Ci-Cs) an aryl group (C6-Cis) or a fused aromatic. 2. Compounds, according to claim 1, of general formula (I) where the compound is selected from the compounds of formula 1 to 4.

3. Compounds, according to claim 1, of general formula (II) where the compound is selected from among the compounds of formula 5 to 8.

4. Compounds, according to claim 1, where the compound is selected from compounds of formula 9 to 11.

5. Procedure for the synthesis of imidazoles fused to carbazolic azahelicenes of general formula (I) and (II) from 3-iodo-2-formyl indoles characterized in that it comprises the following steps: A) Preparation of carbazoles by reaction of the indolic terminal alkyne with 3-iodo-2-formyl indoles. B) Preparation of helical carbazoles through the reaction of iodocarbazoles in the presence of 1,2-diamines and copper catalysis. 6. Synthesis procedure, according to claim 5, of the compounds of formula 5,9, 10 and 11 where the diamine is ortho-amino aniline. 7. Deep blue luminescent emitting dye comprising one or more claimed compounds of general formula (I). 8. Deep blue luminescent emitting dye comprising one or more claimed compounds of general formula (II). 9. Deep blue luminescent emitting dye comprising one or more claimed compounds of formula 1a11. 10. Deep blue luminescent emitting dye comprising optical isomers or individual enantiomers or diastereomers of the claimed compounds or mixtures thereof.