Synthesis, photophysical and electrochemical properties of a new class of fluorescent amidoanthracenophanes

Article abstract of DOI:10.1039/c5ra14357h

Fluorescent amidoanthracenophanes 1, 2, 3 and 4 were obtained from the various aromatic diacid chlorides and diamino precyclophane by simple acylation. All the synthesized amidoanthracenophanes 1, 2, 3 and 4 show three intense fluorescence bands between 401 and 402, 426 and 429, and at 449 to 451 nm, and exhibit two/three oxidation reduction peaks in the cyclic voltammetry which is characteristic of fluorophoric anthracene units.

Full text of DOI:10.1039/c5ra14357h

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Page 1 of 17
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Synthesis, photophysical and elctrochemical properties of a new class of
fluorescent amidoanthracenophanes
Ayyavoo Kannan and Perumal Rajakumar*
Department of Organic Chemistry, University of Madras, Guindy Campus
Chennaiꢀ600 025, India. Eꢀmail: perumalrajakumar@gmail.com
Fax: +91 044 22300488; Tel: +91 044 22351269 ext. 213
Abstract
Fluorescent amidoanthracenophanes 1, 2, 3 and 4 were obtained from the various
aromatic diacidchlorides and diamino precyclophane by simple acylation. All the synthesized
amidoanthracenophanes 1, 2, 3 and 4 show three intense fluorescent bands between 401ꢀ402,
426ꢀ429 and at 449ꢀ451 nm exhibit two/ three oxidation reduction peaks in the cyclic
voltammetry which is characteristic of fluorophoric anthracene unit.
Keywords: Amide, Anthracene, acid chloride, cyclic voltammogram, cyclophane
Introduction
Design and synthesis of new class of photoactive cyclophanes1 with intraannular
amide and anthracene functionality and with various aromatic spacer units are of interest
during recent years. Such cyclophanes have potential applications in supramolecular
chemistry due to their high degree of structural rigidity and are known to form unusually
strained molecules, which can be used for the recognition of specific guest molecules,2 and in
molecular electronic machines,3 and as drug carriers,4 and catalysts in organic synthesis.5 Such
cyclophanes have rigid structure with well defined non collapsible cavity, which influence
the encapsulation of specific guest molecules by nonꢀcovalent interactions,6 host–guest
complexation,7 molecular selfꢀassembly, and specific receptor8 activity. Anthracene based
hybrids 9 have enormous photoactive applications in the field of material chemistry as well as
in biological chemistry. Anthracene is an important building block to develop blue
1

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luminescent dyes due to its merits such as the thermal and electrochemical stability.10 OLEDs
have attracted enormous attention from the scientific community due to their high
technological potential for the next generation of fullꢀcolorꢀflatꢀpanel displays11 and light
emitting applications.12 with excellent stability13 Many kinds of anthraceneꢀfunctionalized
materials have been synthesized and considered for such applications,14 and some of them
were found to be promising blue emitters for OLEDs15 and also function as blueꢀlightꢀ
emitting and holeꢀtransporting materials.16 Nonꢀdoped blue OLEDs with a maximum
efficiency of 1.65 cdA–1 were attained using anthracene moiety.17 The anthracene hybrid
molecules shows strong luminescent behaviour and have been widely used as blueꢀemitting
materials in OLEDs due to their excellent photoluminescence (PL) and electroluminescence
(EL) properties. Anthracene based compounds are used for intrannular charge transfer (CT)
flurescence18 and for sensing metal ion such as Fe2+, alkali, alkali earth and heavy metal ions
as well as anions such as Fꢀ, Clꢀ and Brꢀ.19 Anthracene based cyclophanes can sense
Pyrophosphate ion (PPi)20 which is involved in many vital metabolic and bioenergetic
processes such as DNA and RNA polymerization and for ATP hydrolysis21 and as light active
22
protein cleaving agents
and further they can be used in fuel cells, and as biomimetic
catalysts and in efficient light harvesting antenna devices.
Though we have reported from our lab the synthesis and selective ion separation of
various biologically useful amide cyclophanes,23 the preparation of new class of cyclophanes
called amidoanthracenophanes remain unexplored. We wish to report the synthesis,
photophysical and electrochemical properties of new class of cyclophanes 1, 2, 3 and 4
referred as amidoanthracenophanes (Fig. 1).
2

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O
O
O
O
N
HN
S
NH
S
HN
S
NH
S
2
1
OC7H15
O
O
S
O
O
HN
S
NH
S
HN
S
NH
S
4
3
Fig. 1. Structure of new class of cyclophanes 1, 2, 3 and 4 called amidoanthracenophanes
Result and discussions
Synthesis of amidoanthracenophanes 1, 2, 3 and 4 begins from the reaction of 2ꢀ
aminobenzenethiol 6 with 9, 10ꢀchloromethyl anthracene 5 in the presence of KOH and
catalytic amount of TBAB (10 mg) in a mixture of toluene/ H2O (1:1) to give the
precyclophane diamine 7 in 86% yield (scheme 1). The 1H NMR spectrum of precyclophane
diamine 7 displayed a broad singlet at δ 4.33 for amine protons, a singlet at δ 4.93 for S-CH2
protons in addition to the signals for aromatic protons. In the 13C NMR spectrum,
precyclophane diamine 7 showed the S-CH2 carbons at δ 32.9 in addition to the signals for
aromatic carbons. The mass spectrum (ESIꢀMS) of precyclophane diamine 7 showed the
molecular ion peak at m/z 542. Further, the structure of the precyclophane diamine 7 was also
confirmed from elemental analysis.
3

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O
O
8
Cl
Cl
(1.0 equiv.)
1
ii
O
O
N
Cl
9
Cl
(1.0 equiv.)
2
ii
H2N
S
NH2
S
OC7H15
Cl
i
Cl
O
O
10
Cl
7
Cl
5
(1.0 equiv.)
3
ii
O
O
S
Cl
Cl
11
(1.0 equiv.)
4
ii
Scheme 1 Reagents and conditions: (i) 2ꢀaminothiophenol 6 (2.1 equiv.) KOH, TBAB (cat),
tolouneꢀH2O, 12 h, 7 (86%); (ii) TEA, DCM (dry), 15 h, 1 (62%), 2 (63%) 3 (62%) and 4
(64%).
The diacid chlorides 8, 9, 10 and 11 were prepared from the corresponding
dicarboxylic acid using thionyl chloride (SOCl2) as per the reported procedure.24 The
fluorescent amidoanthracenophanes 1, 2, 3 and 4 were synthesized in 62%, 63%, 62% and
64% yields, respectively by the reaction of 1 equiv. of precyclophane diamine 7 with 1 equiv.
of isophthaloyl chloride 8/ 2,6ꢀpyridine dicarboxylic acid chloride 9/ 5ꢀnꢀheptyloxy
isophthaloyl chloride 10/ 2,5ꢀthiophene dicarboxylic acid chloride 11 in the presence of dry
1
DCM, TEA under nitrogen atmosphere for 15 h at room temperature. In H NMR spectrum,
amidoanthracenophane 2 exhibited a sharp singlet at δ 4.96 for SꢀCH2 protons and a singlet at
δ 9.06 for the amide NH protons in addition to the aromatic proton signals. The 13C NMR
spectrum of amide cyclophane 2 showed SꢀCH2 carbon at δ 34.5 and amide carbonyl carbon
at δ 160.9 in addition to the signals for the aromatic carbons. The mass spectrum (ESIꢀMS) of
4

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2 showed the molecular ion peak at m/z 583 (M+). Further, the structure of the amide
cyclophane 2 was also confirmed from elemental analysis.
In the 1H NMR spectrum, the fluorescent amidoanthracenophane 3 showed triplet at δ
0.90 for the alkyl methyl protons, a sharp singlet at δ 4.81for SꢀCH2 protons and a singlet at δ
8.49 for the amide NH protons in addition to signals for other aliphatic and aromatic protons.
The 13C NMR spectrum of amide cyclophane 3 showed Sꢀ CH2 carbon at δ 35.9 and amide
carbonyl carbon at δ 164.8 in addition to the signals for other aliphatic and aromatic carbons.
The mass spectrum (ESIꢀMS) of 3 showed the molecular ion peak at m/z 696 (M+). Further,
the structure of the amide cyclophane 3 was also confirmed from elemental analysis.
Similarly, the structure of the fluorescent amidoanthracenophanes 1 and 4 was confirmed
from the spectral and analytical data.
Optical, photophysical, laser and salvatochromism properties of the anthracene bridged
fluorescent amidophanes.
The optical and photophysical properties of the anthracene bridged fluorescent
amidoanthracenophanes 1, 2, 3 and 4 are presented in Table 1. The absorption spectra (1×10ꢀ5
M) and fluorescence spectra (1×10ꢀ5 M) of the anthracene bridged fluorescent
amidoanthracenophanes 1, 2, 3 and 4 in DCM are shown in Fig. 2. The electronic absorption
spectra of anthracene bridged fluorescent amidophane 1, 2, 3 and 4 shows three intense
absorption bands between 373ꢀ375, 393ꢀ394 and 415ꢀ418 nm due to the πꢀπ* transitions of
anthracence unit. Anthracene bridged fluorescent amidophane 1, 2, 3 and 4 when excited at
370 nm gave three fluorescent emission bands between 401ꢀ402, 426ꢀ429 and 449ꢀ451 nm.
All the synthesized fluorescent amidophanes 1, 2, 3 and 4 showed the strong fluorescence
intensity between 426ꢀ429 nm (Figure 2), due to the presence of anthracene chromoporic
unit in the cyclic system. This confirms that all the cyclophanes have excellent fluorescence
property.
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Figure 2. Absorption and emission spectrum of fluorescent amidophanes 1, 2, 3 and 4
Table 1. Optical, photophysical and electrochemical parameters for the fluorescent
amidophanes 1, 2, 3 and 4 in DCM at 1X10ꢀ5 M concentration.
Life Time (τ) (ns)
τ 2 τ 3
Cyclic
Voltammetry
Quantum
yield
Entry
No
λ
abs max (nm) λemmax
τ1
χ2
Epa
Epc
(nm)
(Φf)
375 (113000),
394 (126000),
416 (110000)
373 (85000),
394 (129000),
418 (132000)
374 (94000),
393 (129000),
416 (123000)
373 (102000),
393 (139000),
415 (136000)
1
2
3
4
401,
426 &
449
0.52 2.78 7.13 1.16 ꢀ0.49, ꢀ0.77,
0.57 1.20
0.29
0.21
0.33
0.11
402,
427 &
450
ꢀ0.51, ꢀ0.75,
0.49 2.75 6.40 1.16 0.57,
1.12
0.42,
1.15
401,
428 &
450
0.84 1.49 7.46 1.08 ꢀ0.55, ꢀ0.70,
0.55 0.62
401,
429 &
451
0.43 1.93 7.39 1.19 0.28, ꢀ0.42,
0.54 0.71
Life time decay analysis was carried out with all the fluorescent amidophanes 1, 2, 3
and 4 by using Iglesia Bautista Horeb (IBH), TimeꢀCorrelated Single Photon Counting
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(TCSPC) technique on excitation at 370 nm in DCM as solvent. The fluorescence decay fits
as triꢀexponential with life time τ1, τ2 and τ3. The life time decay of the amidophanes 1, 2, 3
and 4 is shown in Table 1. The fluorescence decay (Fig. 3) of amidophanes 1, 2, 3 and 4
shows a longer relaxation time τ2 and τ3 for the 2nd & 3rd exponential and also shorter
relaxation time τ1 for the 1st exponential.
Figure 3. Fluorescence decay of amidophanes 1, 2, 3 and 4 (IRF=Instrument Response
Function).
The solvatochromism of the synthesized fluorescent amidophanes 1, 2, 3 and 4 was
carried out by using UVꢀvis and flourescence spectroscopy. UVꢀvis and fluorescence spectra
were measured for all the synthezied cyclophanes in five different solvents viz toluene,
dichloromethane (DCM), ethyl acetate (EA), acetonitrile (CH3CN) and tetrahydrofuron
(THF) as shown in Fig. 4 for amidophane 1 and as shown in Fig. S1, S2 and S3 (ESI) for
amidophanes 2, 3 and 4. Summary of the photophysical and electrochemical data of all the
compounds are given in Table 2. There is no obvious solvatochromism in the absorption
spectra. These four compounds exhibit the rather similar absorption bands in the range of
373–418 nm, which were assigned to the π–π* transition of the characteristic vibrational
structures of the isolated anthracene groups.24 In comparison with the absorption spectra, the
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emission spectra are sensitive to the polarity of the solvent as shown in fig 4 for cyclophane 1
in various solvents and the other amidophanes 2, 3 and 4 are shown in ESI (fig S1, fig S2 and
fig S3 in). In the presence of varous solvents like toluene, ethyl acetate, acetonitrile and THF
in absorption and fluorescence spectrum, the peaks are redꢀshifted and broadened spectra
were found compare with DCM for all the compounds. This phenomenon can be explained
by the solvent stabilization of the excited state and dipolar interactions between anthracene
amidopahnes and the polar solvents.26
Figure 4. The salvatochromism of the fluorescent amidophane 1 of absorption and emission
spectrum.
Electrochemical properties of fluorescent amidophanes 1, 2, 3 and 4
The electrochemical behaviour of the fluorescent amidoanthracenophanes 1, 2, 3 and
4 was studied by cyclic voltammetry with glassy carbon (GC) electrode as working electrode,
Pt wire as auxiliary electrode and Ag/AgCl as the reference electrode with 0.1 M TBAP as a
supporting electrolyte in dry DCM. The cyclic voltammogram shows the anodic and
cathodic peak potential response for all the fluorescent amidoanthracenophanes
corresponding to the electrochemical oxidation and reduction process. The fluorescent
amidoanthracenophanes 1shows two oxidation potential at ꢀ0.77 and 1.20 as well as two
reduction peaks at ꢀ0.49 and 0.57. From this study, the synthesized fluorescent amidophanes
1 shows electrochemical property, which can be attributed due to the presence of fluorophoric
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anthracene unit. The electrochemical properties are altered due to the presence of aromatic
unit such as benzene is present at the intraannular position of the cyclophane. The cyclic
voltammogram of the amidecyclophane 2,3 and 4 was shown in SI (Figure S4 and S4a)
Figure 4. Cyclic voltammograms of fluorescent amidophanes 1 in DCM at room temperature
(scan rate at 100 mV sꢀ1) and 0.1 M TBAP as a supporting electrolyte in dry DCM.
Experimental
All reagents were commercially available and used as such unless otherwise
stated. Analytical TLC was performed on commercial Merk plates coated with Silica Gel
GF254. Analytical samples were obtained by silica gel chromatography, using silica gel of
100ꢀ200 mesh and elution with the solvent system as mentioned under each experimental
section. The melting points were determined by using a Metler Toledo melting point
apparatus by open capillary tube method and were uncorrected.1H and 13C NMR spectra were
recorded on a 300 MHz BRUKER AVANCE (75 MHz for 13C NMR,) spectrometer.
Chemical shifts values are reported in δ ppm relative to internal standard tetramethylsilane
(TMS, δ 0.00). 13C chemical shifts (ppm) are reported in δ relative to CDCl3 (center of triplet,
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δ 77.23). The spin multiplicities are indicated by the symbols s (singlet), d (doublet), t
(triplet), q (quartet), m (multiplet) and br (broad), dd (doublet of doublets). UVꢀVis
absorption spectra were measured with a Perkin–Elmer Lambda 35 UVꢀvis spectrometer,
Emissions were recorded on Perkin–Elmer Lambda 45 fluorescence spectrometer and
fluorescence quantum yield was determined by exciting the sample at 370 nm with the use of
quinine sulfate as the standard (Φf = 0.546 in 0.1 N H2SO4) recorded on HORIBA JOBIN
YVON Fluoromaxꢀ4P spectrometer under without N2 atmosphere. Fluorescence decays were
recorded by using an IBH timeꢀcorrelated singleꢀphoton counting spectrometer. The Mass
spectra were obtained by EIꢀMS spectra on JEOL DXꢀ303 mass spectrometer from CLRI,
adyar and C, H and N values are obtained PerkinꢀElmer 240B elemental analyzer from NCL
pune. Cyclic voltammetry measurements were performed in a conventional three electrode
system on a CHI model 1100A series electrochemical analyzer (CH Instrument, Austin, TX).
The measurements were based on a three electrode system, with a glassy carbon (GC)
electrode (of geometric area 0.07 cm2) being used as the working electrode, a Pt wire in the
form of a spiral (with a high geometrical surface area 20 cm2) being used as the auxiliary
electrode and Ag/AgCl as the reference electrode with a scan rate of 100 mV sꢀ1.
Tetrabutylammonium perchlorate (TBAP) 0.1 M is used as supporting electrolyte for cyclic
voltammetry studies.
Preparation of 9, 10 dichloromethylanthracene 5
To a stirred solution of anthracene (1.78 g, 10 mmol), anhydrous ZnCl2 (1.64 g, 12
mmol), and paraformaldehyde (1.50 g, 50 mmol) in dioxane (20 mL) was slowly added
concentrated aqueous hydrochloric acid (1N, 40 mL) at room temperature. After addition, the
mixture was refluxed gently for 3 h and allowed to stand for 16 h at room temperature. The
resulting fine granular solid was separated by filtration and washed with H2O and dioxane to
afford the crude product. The crude product was recrystallized from toluene to give 5 as
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1
yellowish solid. Yield : 65%, H NMR : (300 MHz, CDCl3): δH 5.77 (s, 4H), 7.74ꢀ7.77 (m,
4H), 8.53ꢀ8.55 (m, 4H). 13C NMR :(75 MHz, CDCl3):
MS (EI): m/z 275 (M+).
δC 52.6, 123.5, 125.7, 127.2, 129.4.
Synthesis of Precyclophane 7
A mixture of 2ꢀaminobenzenethiol (2.1 equiv.), 9,10ꢀchloromethyl anthracene 7 (1
equiv.), TBAB (5 mg), KOH (2 equiv.), in toluene (20 mL) and water (20 mL) is stirred for
overnight at room temperature. Toluene layer was separated, washed with 5% KOH solution
(2 x 10 mL) and with water (20 mL). The toluene layer after drying over Na2SO4, was
evaporated under vacuum to give the dark yellow colored residue, which was purified by
column chromatography using chloroform: hexane (4:1) as eluting solvent to give 7 as pale
o
1
yellow colour solid. Yield: 86 %, MP : 132ꢀ134 C, H NMR : (300 MHz, CDCl3): δH 4.33
(bs, 4H), 4.93 (s, 4H), 6.60ꢀ6.69 (m, 2H), 7.00 (d, J= 8.1 HZ, 2H), 7.09ꢀ7.15 (m, 2H), 7.35 (d,
J= 7.8 HZ, 2H), 7.45ꢀ7.48 (m, 4H), 8.26ꢀ8.29 (m, 4H). 13C NMR: (75 MHz, CDCl3): δC
32.9, 114.9, 118.3, 118.6, 124.8, 125.6, 129.7, 129.8, 130.8, 136.6, 148.7. MS (EI): m/z 452
(M+). Elemental Anal. Calcd for C28H24N2S2 : C, 74.30, H, 5.34, N, 6.19%. Found : C, 74.26,
H, 5.31, N, 6.15%.
General procedure for the formation of cyclophanes
2ꢀ((10ꢀ((2ꢀAminophenylthio)methyl)anthracenꢀ9ꢀyl)methylthio)benzenamine,
7
(1
equiv., 1.0 mmol ) 7 was dissolved in dry CH2Cl2 and the solution was cooled to 0 °C. Et3N
(0.61 mL, 4.4 mmol) and then various aromatic dicarboxylic acid chlorides (1.1 equiv., 1.1
mmol) in dry CH2Cl2 (30 mL) were added. The mixture was allowed to warm up to room
temperature and stirred under nitrogen atmosphere for 15 h. The dark yellow solution was
washed with 0.5 M HCl (100 mL) and water (3 x 100 mL) and the organic layer was then
collected, dried over Na2SO4 and concentrated to dryness. The dark yellow solid residue
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obtained was purified by column chromatography using chloroform: methanol as eluting
solvent.
Amidoanthracenophanes 1
Amidoanthracenophanes 1 was synthesized as a light yellow solid from 2ꢀ((10ꢀ((2ꢀ
Aminophenylthio)methyl)anthracenꢀ9ꢀyl)methylthio)benzenamine (0.5 g, 1.1 mmol ) 7 and
1,3ꢀbenzenedicarboxylic acid chloride 8 (0.25 g, 1.21 mmol) by using general procedure;
o
1
Yield : 62%, MP : 165ꢀ168 C, H NMR : (300 MHz, CDCl3): δH 4.82 (s, 4H), 7.18ꢀ7.21
(m, 4H), 7.26ꢀ7.31 (m, 2H), 7.37ꢀ7.42 (m, 2H), 7.44ꢀ7.49 (m, 3H), 7.77 (s, 1H), 7.80ꢀ7.83(m,
4H), 7.99 (d, J=7.5 HZ, 2H), 8.20 (d, J= 8.1 HZ, 2H), 8.74 (s, 2H). 13C NMR : (75 MHz,
CDCl3): δC 35.9, 121.1, 121.9, 124.1, 124.6, 125.1, 125.9, 129.0, 129.3, 130.4, 130.9, 131.1,
135.5, 137.4, 140.7, 164.8. MS (EI): m/z 582 (M+). Elemental Anal. Calcd for C36H26N2O2S2 :
C, 74.20, H, 4.50, N, 4.81%. Found: C, 74.16, H, 4.46, N, 4.77%.
Amidoanthracenophanes 2
Amidoanthracenophanes 2 was synthesized as light yellow solid from 2ꢀ((10ꢀ((2ꢀ
Aminophenylthio)methyl)anthracenꢀ9ꢀyl)methylthio)benzenamine (0.5 g, 1.1 mmol ) 7 and
Pyridine dicarboxylic acidchloride 9 (0.247 g, 1.21 mmol) by using general procedure; Yield
o
1
: 63%, MP : 210ꢀ214 C, H NMR : (300 MHz, CDCl3): δH 4.96(s, 4H), 7.00ꢀ7.04 (m, 4H),
7.18 (t, J= 9.0 HZ, 2H), 7.23ꢀ7.29 (m, 2H), 7.59 (d, J= 8.1 HZ, 2H), 7.94 (d, J= 7.2 HZ,
2H), 7.98ꢀ8.01 (m, 4H), 8.03 (s, 1H), 8.32 (d, J= 7.8 HZ, 2H), 9.06 (s, 2H). 13C NMR : (75
MHz, CDCl3): δC 34.5, 122.4, 124.4, 125.1, 125.2, 126.1, 127.3, 128.9, 129.8, 130.8, 138.3,
138.6, 140.1, 148.5, 160.9. MS (EI): m/z 583 (M+). Elemental Anal. Calcd for C35H25N3O2S2 :
C, 72.02, H, 4.32, N, 7.20%. Found : C, 71.09, H, 4.29, N, 7.15%.
Amidoanthracenophanes 3
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Amidoanthracenophanes 3 was synthesized as a light yellow solid from 2ꢀ((10ꢀ((2ꢀ
Aminophenylthio)methyl)anthracenꢀ9ꢀyl)methylthio)benzenamine (0.5 g, 1.1 mmol ) 7 and
5ꢀnꢀheptyloxy dicarboxylic acid chloride 10 (0.239 g, 1.21 mmol) by using general
procedure; Yield : 62%, MP : 165ꢀ167 oC, 1H NMR : (300 MHz, CDCl3):
Hz, 3H ), 1.32 (s, 8H), 1.77ꢀ1.81 (m, 2H), 3.98 (t, = 6.0 Hz, 2H), 4.81 (s, 4H), 7.19ꢀ7.22
δH 0.90 (t, J = 5.1
J
(m, 4H), 7.25 (s, 3H), 7.43ꢀ7.47 (m, 4H), 7.79ꢀ7.82 (m, 4H), 7.98 (d, J= 7.6 HZ, 2H), 8.17 (d,
J= 8.4 HZ, 2H), 8.49 (s, 2H). 13C NMR: (75 MHz, CDCl3): δC 14.1, 22.6, 25.9, 29.1, 31.8,
32.9, 35.9, 68.6, 113.7, 116.6, 121.2, 124.2, 124.5, 124.8, 125.9, 129.0, 129.4, 131.0, 137.0,
137.4, 140.7, 159.7, 164.8. MS (EI): m/z 696 (M+), Elemental Anal. Calcd for C43H40N2O3S2
:C, 74.11, H, 5.79, N, 4.02%. Found : C, 74.06, H, 5.76, N, 3.98%.
Anthraceneamide cyclophane 4
Amidoanthracenophanes 4 was synthesized as a light yellow solid from 2ꢀ((10ꢀ((2ꢀ
Aminophenylthio)methyl)anthracenꢀ9ꢀyl)methylthio)benzenamine (0.5 g, 1.1 mmol ) 7 and
thiophene 2,5ꢀdicarboxylic acid chloride 11 (0.25 g, 1.21 mmol) by using general procedure;
o
1
Yield : 64%, MP : 198ꢀ203 C, H NMR : (300 MHz, CDCl3): δH 5.00 (s, 4H), 7.31 (d, J=
7.5 HZ, 2H), 7.40ꢀ7.43 (m, 4H), 7.53 (t, J= 7.5 HZ, 2H), 7.60 (s, 2H), 7.96 (d, J= 7.8 HZ, 2H),
7.99ꢀ8.02 (m, 4H), 8.42 (d, J= 8.1 HZ, 2H), 8.69 (s, 2H). 13C NMR : (75 MHz, CDCl3): δC
36.5, 120.4, 124.6, 124.8, 125.1, 126.5, 129.2, 131.1, 132.2, 132.6, 137.0, 139.4, 140.2,
158.7. MS (EI): m/z 588 (M+), Elemental Anal. Calcd for C34H24N2O2S3: C, 69.36, H, 4.11,
N, 4.76%. Found: C, 69.31, H, 4.07, N, 4.71%.
Fluorescence measurement
The photoluminescence (PL) spectra of the synthesized fluorescent
amidoanthracenophanes 1, 2, 3 and 4 are recorded under without N2 atmosphere in 1×10ꢀ5 M
concentration in DCM and excited at 370 nm.
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DOI: 10.1039/C5RA14357H
Conclusion
In conclusion, all the fluorescent amidophanes 1, 2, 3 and 4 were successfully
synthesized in excellent yield. All the amidophanes are fluorescent in nature and the optical,
photophysical and electrochemical properties are altered due to the presence of various
aromatic units at the intraannular position of the cyclophane. All the amidophanes emit blue
light under ultra violet irradiation, such property is very useful for chemical sensors and for
exhibiting OLED properties. The sensing ability of such amidophanes against various metal
cations, anions and also biomolecules like DNA is underway.0
Supporting Information
The detailed spectrum of optical and fluorescence of the synthesized amidopahes 2, 3
and 4 and also optical and photophysical parameters. The 1H NMR and 13C NMR details are
present in the electronic supporting information (ESI).
Acknowledgment
The author thanks CSIR, New Delhi, India, for financial assistance and DSTꢀFIST for
providing NMR facility to our department. AK thanks CSIR and UGC, New Delhi, for
fellowship.
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