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A substituted BF2-chelated tetraarylazadipyrromethene as an intrinsic

dual chemosensor in the 650–850 nm spectral range
John Killoran,a Shane O. McDonnell,a John F. Gallagherb and Donal F. O’Shea*a
Received (in Durham, UK) 24th August 2007, Accepted 13th November 2007
Published on 20 November 2007. Downloaded by University of Illinois at Chicago on 24/10/2014 23:01:32.

First published as an Advance Article on the web 20th November 2007

DOI: 10.1039/b713020a

The synthesis and spectral analysis of a new class of long wavelength intrinsic fluorosensor is
reported. Chemosensor performance reveals large off/on fluorescence intensity responses to acid
analyte with low response to microenvironment polarity. Application to ratiometric fluorescence/
UV-visible analysis is outlined.

Introduction Herein, we report the synthesis and chemosensor character-

istics of a double amine receptor substitution pattern (Fig. 1
The development of organic chromophores with spectral Ar1 and Ar2 = p-(CH3)2NC6H4). Based upon the results of an
properties in the near-infrared (NIR) and visible red spectral earlier model system, it was envisaged that substituting the
regions continues to attract a sustained research interest. New parent chromophore molecule with two intrinsically connected
chromophore scaffolds with controllable photophysical pro- amine donors would produce a more advanced molecular
perties in the 650–900 nm spectral region offer potential for assembly which could generate pronounced photophysical
exploitation in a diverse range of material and biological changes as a result of a substrate recognition event by the
applications, such as optical data storage,1 photoconductors,2 amine substituents.12 It was anticipated that this electron
electrochromic devices,3 chemosensors,4 immunoassay labels donor–acceptor double amine receptor–chromophore design
and bioconjugated probes,5 and in vitro and in vivo imaging would undergo pronounced spectral changes due to variance
agents.6 Specifically, NIR dyes are suitable as in vitro and in the internal charge transfer (ICT) properties of the system in
in vivo biomedical diagnostic agents due to efficient penetra- response to acid analyte. A study of the analyte responsive
tion of light through tissue and the low auto-fluorescence of photophysics of this system would provide the framework for
endogenous chromophores in this spectral region.7 Despite the more elaborate receptors to detect other analytes.13
optical benefits of utilising this spectral region for analytical
techniques, there is a surprising scarcity of organic compounds
which have the desired absorption and emission properties. In Results and discussion
spite of their poor photostability and lengthy synthetic routes,
Synthesis
the cyanine dyes have to date been the most widely utilised
class for applications in this spectral region.8 The synthesis of our target compound 1a was achieved in a
We are currently interested in devising new chemosensors routine four step route from acetophenone and 4-dimethyl-
based upon the BF2-chelated-azadipyrromethenes, which are aminobenzaldehyde.14 Condensation of the aldehyde with
readily synthesised, show high photostability, and are amen- acetophenone gave the a,b-unsaturated ketone 2 which
able to peripheral functionalisation to engender higher-order following conjugate addition of nitromethane provided the
function. 1,3-diaryl-4-nitrobutan-1-one 3 in 87% yield after recrystalliza-
The BF2 chelated-tetraarylazadipyrromethene 1 and related tion (Scheme 1).
structural analogues have recently been reported as a class of Generation of the tetraarylazadipyrromethene 4 was
chromophore with high absorption extinction coefficients achieved by heating 3 with ammonium acetate in ethanol for
(70–80  103 M 1 cm 1) and fluorescence quantum yields 48 h during which time the product precipitated from solution.
(0.23–0.36) between 650 and 750 nm (Fig. 1).9 We have also Filtration of the precipitate from the crude reaction mixture
shown that with selective positioning of prototype amine gave the pure product as a dark blue solid in 45% yield. A
receptors this class can be utilized as a visible red and/or higher yield could be obtained if butanol was used as solvent
NIR chemosensor operating by either a photoinduced electron (50%) but silica gel chromatography was required for purifi-
transfer (PET) or a charge transfer (CT) mechanism.10 cation. Compound 4 was converted to our targeted structure
Subsequently this fluorophore class has been successfully
adapted as chemosensors for analytes such as saxitoxin and
mercury(II).11

a
Centre for Synthesis and Chemical Biology, School of Chemistry and
Chemical Biology, University College Dublin, Belfield, Dublin 4,
Ireland. E-mail: [email protected]; Tel: +353-(0)1-7162425
b
School of Chemical Sciences, Dublin City University, Dublin 9,
Ireland Fig. 1 BF2-chelated tetraarylazadipyrromethenes.

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Fig. 3 Compound 1a (molecule A) with displacement ellipsoids

depicted at the 30% probability level. Weak intramolecular interac-
Scheme 1 tions are present involving N1A, F1A/F2A and neighbouring
aromatic C–H groups (as noted in the text).
1a by reaction with boron trifluoride diethyletherate and
diisopropylethylamine in dichloromethane for 24 h. An iso- only significant intermolecular interactions involve the rela-
lated purified yield of 53% was obtained following chromato- tively weak C–H


N/F and C–H


p(arene) interactions of
graphy on silica gel. which two are noteworthy namely C42B–H42B


Cg1
[H42B


Cg1 is 2.79 Å, angle of 1511, C42B


Cg1 is
X-Ray crystallographic study 3.649(6) Å, Cg1 = centroid C11A–C16A] and
C47B–H47E


Cg2i [H47E


Cg2i is 2.82 Å, angle of 1371,
The crystal and molecular structure of 1a have been deter-
C47B


Cg2i is 3.604(6) Å, Cg2 = centroid C31B–C36B,
mined by single-crystal X-ray diffraction both at 294 and
symmetry operation i = 1 x, y, 1 z] (Fig. 2). These
120 K: only the latter results will be discussed. Compound
weak interactions and packing forces combine to enforce
1a crystallizes in the triclinic system, space group (P
1, no. 2)
subtle differences between molecules A and B in the solid state.
with two molecules (A and B) in the asymmetric unit and
The interactions in 1a mainly comprise intramolecular aro-
though broadly similar in conformation there are quite distinct
matic C–H


F involving the BF2 moiety. The interactions for
differences in the bond and torsion angles (Fig. 2 and 3). The
molecule A are H16A


F1A at 2.16 Å (C16A


F1A is
3.046(6) Å, angle of 1521) and H32A


F2A at 2.15 Å
(C32A


F2A is 3.006(7) Å, angle of 1501): molecule B is
similar with H16B


F1B 2.17 Å (C16B


F1B is 3.020(5) Å,
angle of 1501) and H32B


F2B 2.20 Å (C32B


F2B is
3.047(6) Å, angle of 1481) (Fig. 3).
The NMe2 groups are representative with a separation of ca.
0.6 Å for the N


N non-bonded distances of 7.617(7) and
7.041(6) Å in molecules A and B, respectively. There are no
discernible differences in the internal bond lengths between
molecules A and B primarily due to the data quality: the esds
are large and preclude meaningful one-for-one comparisons.
However, there are distinct differences in atom separation
distances in the molecules as a result of subtle conformational
differences. In molecule A, the C3A


N24A and
C8A


N44A distances are 5.682(8) and 5.649(7) Å [5.666(8),
5.646(7) Å in B], but this is not significant for elongation or
shortening along the C–C6H4–NMe2 groups in either mole-
cule. A more distinct difference is the B


N distances for
B1A


N24A/N44A being 9.215(9)/9.209(8) Å (similar to
Fig. 2 A view of molecules A and B of 1a with atoms drawn as their B1B


N44B, 9.190(8) Å) but longer by 0.08 Å in comparison
van der Waals spheres highlighting the C–H


p(arene) interactions to B1B


N24B at 9.128(9) Å. Therefore, molecules A and B
between A and B. differ subtly and examination of the N


N distances between

484 | New J. Chem., 2008, 32, 483–489 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008
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the para-disubstituted C–C6H4–NMe2 rings highlights these larger pyramidalisation at the N atom (greater N


C3 plane
subtleties with N24A


N44A 7.617(7) Å and N24B


N44B distance). Therefore, the resulting and decreasing ability of the
7.041(6) Å, indicating an opening up or bending of these lone pair of electrons on the N atom to participate in
groups relative to one another (the N24


N1


N44 angles conjugation with the aromatic C6 group is observed through
in A, B are 70.04(7), 65.39(7)1). The distortion can also be (a) longer C–N bond lengths, (b) increased twisting from co-
observed in the torsion angles where the N24


C3


; planarity and (c) increased N atom pyramidalisation. These
C8


N44 angles for A, B differ by 101 ( 0.83(13)1 in A and effects at the C6–NMe2 chromophore can have a profound
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9.20(14)1 in B). effect on the photophysical properties of a system in the solid

The three central fused-rings of 1a (comprising 12 atoms, 4 state and in the solution if there is a measure of steric influence
of which are common to the five/six-membered fused-ring, restricting rotation of the NMe2 and other pendant groups.
discounting the F atoms) are essentially co-planar (though
with a slight ‘ruffling’) with the maximum deviation for any Spectroscopic study
non-hydrogen atom in either of the two five-membered C4N or
the six-membered BC2N3 rings in molecules A, B is for C1A, Aqueous solutions of 1a, suitable for pH titrations, were made
C3A by 0.020(3) Å in C4N and 0.026(3) Å for C1B in the using the emulsifier Cremophor EL (CrEL), a commonly used
BC2N3 core in B (Fig. 4). non-ionic surfactant exploited as a formulating agent for
The range of interplanar angles between the five- and six- poorly water-soluble pharmaceuticals.15 Examination of the
membered [C4N/BC2N3] rings is from 4.6(3) to 6.4(3)1, high- excited state response of aqueous formulated solutions of 1a to
lighting the essentially co-planar nature of the 12 atoms in the varying acidic conditions were carried out. We were pleased to
central fused-ring moieties.9 The C6H5 (phenyl) ring orienta- observe virtually complete quenching of the fluorescence in the
tions differ with angles of 17.4(3)1 (A) and 13.9(2)1 (B) for the pH range where the amine receptor remained unprotonated
[C11–C16]/[C31–C36] planes, while the NMe2 substituted C6 (Fig. 5, red trace). Upon protonation, the fluorescence spec-
ring planes are oriented at 10.5(3)1 (A) and 9.4(2)1 (B). trum showed a strong proton induced fluorescence enhance-
The four NMe2 (molecules A and B) groups differ consider- ment with a wavelength of maximum fluorescence at 685 nm
ably, both in their twist angles with respect to the C6 rings, but (Fig. 5, green trace). A sigmoidal plot of pH vs. fluorescence
also due to pyramidalisation effects at the N atoms. A con- intensity predicted an apparent pKa of less than 1.0 (Fig. 5,
venient measure of pyramidalisation is the distance from the N inset). This value is indicative of a strong coupling of the
atom to the C3, [CMe/Carom/CMe], plane (this is 0.0 Å when the receptor and fluorophore sub-units, though it should be noted
N and 3C atoms are co-planar). In 1a, the range is from that pKa values in a micellar microenvironment are often
0.003(5) Å (for N44B


C3) to 0.137(6) Å (for N24A


C3), lower than might be anticipated. Significantly, the enhance-
indicating a range of geometries within the NMe2 groups. A ment of fluorescence intensity was greater than 250-fold
Cambridge Structural Database (CSD) analysis for between the chemosensor off and on positions. The co-planar-
C–C6–NMe2 moieties in a range of 300+ molecules shows a ity of the receptors and the fluorophore of chemosensor 1a
direct correlation between increasing C–NMe bond length facilitates a donor–acceptor CT interaction between the anili-
(increasing single bond character), increasing C6/NMe2 twist no lone pairs of electrons and the fluorophore in the unpro-
angle (from 01) and pyramidalisation at the N atom (increas- tonated state, which gives rise to highly efficient quenching of
ing N


C3 plane distance).12 In 1a, the longest C–NMe the fluorescence emission. This is further endorsed by analysis
distance is 1.384(7) Å for C24A–N24A [range of of the absorption spectrum of 1a. Unprotonated 1a displays
1.353(7)–1.373(6) Å for the three remaining C–N distances strong CT characteristics with three bands between 500 and
involving N44A, N24B, N44B]: a corresponding twist of
14.0(7)1 at N24A [2.1(5)–4.3(4)1 at N44A, N24B, N44B], and
a N24A


C3 distance of 0.137(6) Å [0.003(5)–0.065(6) Å for
N44A, N24B, N44B


C3]. In 1a our results follow the ob-
served trend observed in the CSD analysis for C–C6–NMe2
systems described above. Increasing single bond character in
the C–N bond (C–N lengthening) correlates well with in-
creased twisting away from C6/NMe2 co-planarity and with

Fig. 5 pH responsive fluorescence spectra of 1a (excitation 630 nm,

1  10 6 M) in H2O/CrEL, INaCl = 150 mmol L 1. The pH values in
Fig. 4 A view along the B


N axis of the central core non-hydrogen order of decreasing intensity are 0.25, 0.40, 0.55, 0.65, 0.80, 0.95, 1.15,
atoms in 1a (molecule A) with the hydrogen atoms and peripheral C/N 1.45, 1.90 and 5.45. Inset shows sigmoidal plot predicting an apparent
atoms removed for clarity. pKa value of o1.

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Fig. 8 Ratiometric pH profile of 1a (1  10 6 M) for increase of

6
Fig. 6 pH responsive absorbance spectra of 1a (1  10 M) in H2O/ fluorescence emission at 685 nm (K experimental; — sigmoidal fit)
CrEL, INaCl = 150 mmol L 1. The pH values in order of decreasing and decrease of absorbance band 3 at 789 nm (m experimental; —
intensity of band 3 are 5.45, 1.90, 1.45, 1.15, 0.95, 0.80, 0.65, 0.55, sigmoidal fit) for 1a.
0.40 and 0.25.
The solvent effects on the steady state fluorescence proper-
900 nm (Fig. 6, red trace). Computational deconvolution of ties of 1a and 1a-2H+ are shown in Fig. 9. It is remarkable to
bands 1 and 2 gave maxima at 586 and 620 nm, respectively note that in all the organic solvents studied, polar and non-
(Fig. 7, inset). At pH values greater than 2, no spectral shifts are polar, the fluorescence of 1a is almost completely quenched at
demonstrated by 1a. At pH values o2, bands 1 and 3 can be the respective emission wavelengths of 1a-2H+. This is in
clearly seen to progressively reduce in intensity and a new band contrast to other aniline substituted fluorosensors including
centred at 665 nm for 1a-2H+ appears (Fig. 6, green trace). the aniline substituted 4,4-difluoro-4-bora-3a,4a-diaza-s-inda-
A plot of pH vs. intensity of absorbance bands 1 and 3 cenes (BODIPY class) which exhibit pronounced solvent depen-
clearly demonstrates the double protonation event occurring dent fluorescence quantum yields with high yields recorded in
as a consequence of the two amine receptors. Two sigmoidal non-polar solvents.17 In the less polar solvents cyclohexane,
response curves were calculated for band 1 and 3 (red and chloroform and toluene the unprotonated fluorosensor shows
blue, respectively) predicting an apparent pKa of 1.4 for the a low intensity long wavelength emission ranging from 795 to
first protonation and o1 for the second (Fig. 7) As the pKa of 822 nm, attributed to emission from a CT species. The fluores-
the second protonation was similar to that observed in the cence spectra of 1a-2H+ (TFA added to solution of 1a) show
fluorescence titration this would indicate that it is only upon some solvent polarity dependency with positions of maximum
the second protonation that the fluorescence of 1a is re- fluorescence varying from 677 nm in ethanol to 692 nm in
established. This is clearly demonstrated in a ratiometric plot toluene (Table 1). Full widths at half maximum (FWHM) in all
of disappearance of the absorption band at 789 nm vs. solvents are narrow ranging from 39 to 43 nm. All solvents show
emergence of fluorescence intensity giving an intersect at the excellent fluorescent enhancement factors (FEF) with the un-
pKa value (Fig. 8).16 protonated fluorosensor in the more polar solvents showing
complete quenching of fluorescence.
The absorption spectrum of 1a in organic solvents exhibited
three distinct bands, as was observed for the aqueous

Fig. 7 pH profiles for disappearance of band 1 at 586 nm (red circles,

experimental; line, sigmoidal fit) and band 3 at 789 nm (blue triangles,
experimental; line, sigmoidal fit) of 1a (1  10 6 M). Inset shows Fig. 9 Fluorescence spectra of 1a and 1a-2H+ (TFA added) (excita-
resolved component peaks of the absorbance spectrum generated with tion 630 nm; 5  10 7 M) in acetonitrile (pink), chloroform (yellow),
PeakFit software. cyclohexane (red), ethanol (blue) and toluene (green).

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Table 1 Spectroscopic fluorescence data for 1a-2H+ Table 2 Spectroscopic absorbance data for 1a
a
Solvent lmax/nm FWHM/nm FEF Solventa Band 1/nm Band 2/nm Band 3/nm
Cyclohexane 680 39 180 Cyclohexane 576 613 744
Toluene 692 43 240 Toluene 574 625 763
Chloroform 684 41 4250 Chloroform 572 625 770
Ethanol 677 40 4250 Ethanol 569 631 772
Acetonitrile 679 40 4250 Acetonitrile 572 648 799
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a a
Room temperature. Room temperature.

formulated solutions. The shortest wavelength band was more are quoted in d (ppm) and coupling constants in Hz. Melting
distinct in polar solvents such as acetonitrile than cyclohexane points were determined on a Reichert Thermovar melting
(Fig. 10). The absorbance bands 2 and 3 show a strong positive point platform. Mass spectral analyses were performed on a
solvatochromism in proportion to increasing solvent polarity, Micromass Quattro Micro. IR spectra were recorded on a
bathochromically shifting to 648 and 799 nm in acetonitrile Mattson Instruments Galaxy series FT-IR 3000 spectometer.
when compared to 613 and 744 nm in cyclohexane (Table 2). Absorption spectra were recorded on a Varian Cary 50 UV-
Specifically band 3 exhibited the strongest positive solvato- visible spectrophotometer. Fluorescence spectra were recorded
chromism with increasing solvent polarity, which is a common on a Cary Eclipse spectrofluorometer. Elemental analyses were
characteristic of CT compounds. carried out at the microanalytical laboratory, University
College Dublin.
Conclusions 3-(4-Dimethylaminophenyl)-1-phenylpropenone (2). 4-Di-
In conclusion, we have outlined a facile synthesis to a new methylaminobenzaldehyde (10.0 g, 67 mmol), 1-phenyletha-
class of ratiometric fluorometric and colourimetric chemosen- none (8.05 g, 67 mmol) and three NaOH pellets were dissolved
sor with potential to be exploited and adapted to suit a diverse in methanol (100 mL) and stirred at room temperature until a
range of analytical, imaging and material applications. Speci- heavy precipitate formed (24 h). The precipitate was isolated
fically the low pH range in which sensor response occurs by filtration and washed with cold methanol to give the
indicates that this platform would be suitable for detection product without any further purification, as a bright yellow
of other analytes at physiological pH. Chemosensor perfor- solid of 2 (14.07 g, 84%), mp 110–112 1C. 1H NMR (300 MHz,
mance is excellent with large off/on fluorescence intensity CDCl3) d 7.98–8.02 (m, 2H), 7.79 (d, J = 15.5 Hz, 1H),
responses and low microenvironment polarity effects. In addi- 7.43–7.56 (m, 5H), 7.32 (d, J = 15.5 Hz, 1H), 6.64–6.69 (m,
tion the described synthetic route would readily allow for 2H), 3.00 (s, 6H). 13C NMR (75 MHz, CDCl3) d 190.8, 152.3,
analogues functionalised with other substrate specific recep- 146.0, 139.3, 132.3, 130.6, 128.7, 128.5, 122.9, 117.1, 112.0,
tors to be generated. 40.33. IR (KBr disc): 1649 cm 1. ES-MS: m/z [M + H]+
252.1. Anal. Calc. for C17H17NO: C, 81.24; H, 6.82; N, 5.57.
Found: C, 80.95; H, 6.82; N, 5.49%.
Experimental
3-(4-Dimethylaminophenyl)-4-nitro-1-phenylbutan-1-one (3).
General 3-(4-Dimethylaminophenyl)-1-phenylpropenone 2 (7.0 g, 28.0
1
H NMR spectra were recorded on a Varian FT spectrometer mmol) was dissolved in anhydrous methanol (75 mL), nitro-
at 300 MHz and 13C NMR spectra at 75 MHz, in CDCl3 with methane (8.5 g, 140 mmol) and diethylamine (10.22 g, 140
tetramethylsilane as the internal standard. All chemical shifts mmol) were added, and the reaction was heated under reflux
for 24 h. The reaction mixture was allowed to cool to room
temperature, acidified with 1 M hydrochloric acid and the
resulting precipitate was isolated by filtration. Recrystalliza-
tion from methanol gave the product 3 as a yellow solid (7.6 g,
87%), mp 113–115 1C. 1H NMR (300 MHz, CDCl3) d
7.88–7.92 (m, 2H), 7.51–7.57 (m, 1H), 7.40–7.46 (m, 2H),
7.09–7.14 (m, 2H), 6.63–6.68 (m, 2H), 4.76 (dd, J = 12.3,
6.8 Hz, 1H), 4.61 (dd, J = 12.3, 7.9 Hz, 1H), 4.11 (m, 1H),
3.44 (dd, J = 6.1, 17.0 Hz), 3.36 (dd, J = 7.6, 17.0 Hz), 2.89 (s,
6H). 13C NMR (75 MHz, CDCl3) d 197.5, 150.3, 136.8, 133.6,
128.9, 128.3, 128.3, 126.6, 113.0, 80.2, 42.0, 40.6, 38.8. IR (KBr
disc): 1680, 1546 cm 1. ES-MS: m/z [M + H]+ 313.2. Anal.
Calc. for C18H20N2: C, 69.21; H, 6.45; N, 8.97. Found: C,
69.40; H, 6.39; N, 8.83%.

Fig. 10 Absorbance spectra of 1a (5  10 6 M) in acetonitrile (pink), [3-(4-Dimethylaminophenyl)-5-phenyl-1H-pyrrol-2-yl][3-(4-di-

chloroform (yellow), cyclohexane (red), ethanol (blue) and toluene methylaminophenyl)-5-phenylpyrrol-2-ylidene]amine (4). A
(green). 100 mL round-bottomed flask was charged with 3-(4-di-

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methylaminophenyl)-4-nitro-1-phenylbutan-1-one 3 (1.0 g, lected on an Enraf-Nonius CCD diffractometer at 120 K for

3.21 mmol), ammonium acetate (8.7 g, 112 mmol) and ethanol comparison purposes. A lower R-factor with improved lower
(20 mL) and heated under reflux for 48 hours. During the esds were obtained for a detailed comparison of the two
course of the reaction, the product precipitated from the independent molecules (A and B) in the asymmetric unit. Brief
reaction mixture. The reaction was cooled to room tempera- details of the 294 K dataset of 1a are listed and all further
ture, filtered and the isolated solid washed with cold ethanol discussion refers to the low-temperature 120 K dataset of 1a.
(2  10 mL) to yield the product 4 as a blue–black solid (0.40 All non-hydrogen atoms were refined using anisotropic dis-
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g, 46%), mp 248–250 1C. 1H NMR (CDCl3) d 8.04 (d, J = 9.0 placement parameters and hydrogen atoms were treated as
Hz, 4H), 7.94 (d, J = 7.0 Hz, 4H), 7.40–7.53 (m, 6H), 7.05 riding atoms using the SHELXL97 defaults at the appropriate
(s, 2H), 6.78 (d, J = 9.0 Hz, 4H), 3.04 (s, 6H), (NH not temperatures (294 and 120 K).
observed). 13C NMR (CDCl3) d 154.8, 150.4, 149.8, 143.1,
132.9, 130.5, 129.7, 129.2, 126.6, 122.9, 112.2, 111.9, 40.6. IR Crystal data for 1a at 294 K. C36BF2N5, M = 583.48,
(KBr disc): 3462, 1607 cm 1. lmax (CHCl3): 623 nm. HRMS: triclinic, space group P
1, a = 10.372(10), b = 14.250(13), c
calc. for C36H34N5 [M + H]+: 536.2814, found: 536.2806. = 21.168(15) Å, a = 106.19(8), b = 91.03(11), g = 92.06(9)1,
Anal. Calc. for C36H33N5: C, 80.72; H, 6.21; N, 13.07. Found: V = 3001(5), Z = 4, m = 0.086 mm 1; 1492 reflections with
C, 80.44; H, 6.14; N, 13.10%. I 4 2s(I), R(I 4 2s(I)) = 0.1541, wR(I 4 2s(I)) = 0.3428.

BF2-chelated-[3-(4-dimethylaminophenyl)-5-phenyl-1H-pyrrol- Crystal data for 1a at 120 K. C36BF2N5, M = 583.48,

2-yl][3-(4-dimethylaminophenyl)-5-phenylpyrrol-2-ylidene]amine triclinic, space group P
1, a = 10.2169(7), b = 14.0769(8),
(1a). [3-(4-Dimethylaminophenyl)-5-phenyl-1H-pyrrol-2-yl]- c = 21.0039(15) Å, a = 105.548(2), b = 91.046(2), g =
[3-(4-dimethylaminophenyl)-5-phenylpyrrol-2-ylidene]amine 4 92.138(5)1, V = 2907.0(3), Z = 4, m = 0.088 mm 1; 3569
(0.1 g, 0.186 mmol) was dissolved in dry CH2Cl2 (50 mL), reflections with I 4 2s(I), R(I 4 2s(I)) = 0.0862,
treated with diisopropylethylamine (0.14 mL, 0.78 mmol) and wR(I 4 2s(I)) = 0.1415.
boron trifluoride diethyl etherate (0.14 mL, 1.4 mmol), and
stirred at room temperature under nitrogen for 24 h. The CCDC reference numbers 646558 (294 K) and 646559
mixture was washed with water (2  50 mL), and organic layer (120 K). For crystallographic data in CIF or other electronic
was dried over sodium sulfate and evaporated to dryness. format see DOI: 10.1039/b713020a
Purification by column chromatography on silica gel eluting
with CH2Cl2–hexane (3 : 1) gave the product 1a as a metallic Formulation
brown solid (0.057 g, 53%), mp 258–261 1C. 1H NMR (CDCl3)
Compound 1a (0.005 mmol) was dissolved in THF (1 mL) and
d 8.07 (dd, J = 2.0, 7.0 Hz, 4H), 7.98–8.01 (m, 4H), 7.41–7.46
Cremophor EL (0.1 mL) added. The mixture was sonicated for
(m, 6H), 6.81 (s, 2H), 6.76 (dd, J = 2.0, 7.0 Hz, 4H), 3.07 (s,
30 min followed by removal of the THF under reduced
12H). 13C NMR (CDCl3) d 158.1, 151.3, 145.8, 144.0, 132.7,
pressure. The resulting blue oil was dissolved in 25 mL of
131.1, 130.2, 129.5, 128.5, 121.5, 115.4, 112.2, 40.4. IR (KBr
saline solution (2.19 g NaCl in 250 mL water) and filtered
disc): 1603, 1487 cm 1. EI-MS: m/z 583. HRMS: calc. for
through an Acrodisc 25 mm syringe filter (with 0.2 mm HT
C36H33BF2N5 [M + H]+: 584.2797, found: 584.2813. Anal.
Tuffryn membrane). Final concentration was checked by
Calc. for C36H32BF2N5: C, 74.10; H, 5.53; N, 12.00. Found: C,
UV-visible spectral analysis.
72.52; H, 5.55; N, 11.56%. Crystals were grown by the slow
evaporation of a chloroform solution. UV-visible and fluorescence procedures
X-Ray data collection, structure solution and refinement Solvents used were spectrophotometric grade chloroform,
Data were collected on a Siemens-Bruker P4 diffractometer for which was distilled over potassium carbonate prior to use,
1a at room temperature (294 K) and processed using the spectrophotometric grade acetonitrile and HPLC grade cyclo-
XSCANS suite of programs.18 A low-temperature study was hexane. UV-visible spectra were determined from a 1 cm path
also subsequently undertaken of 1a at 120 K using an Enraf- quartz cell at room temperature. Baseline corrected UV-visible
Nonius diffractometer at the University of Southampton spectra were collected between 250 and 1100 nm. Fluorescence
(ESPRC service) and data were processed using the SMART spectra were determined at room temperature from a 1 cm path
suite of programs.19 Compound 1a crystallizes in the triclinic quartz cell with excitation and emission slit widths of 5 nm.
system (P1, no. 2) with two molecules (A/B) in the asymmetric FEF = fluorescence enhancement factor (IFmax/IFmin).
unit. Solution and refinement was undertaken using
SHELXS97 and SHELXL9720 and the graphics generated
Acknowledgements
with PLATON.21
No disorder is present in 1a but an initial study of a very This work was funded under the Program for Research in
weakly diffracting crystal at room temperature (294 K) pro- Third-Level Institutions administered by the HEA. S. O.
vided only gross conformation details and resulted in a high McD. thanks the Irish Research Council for Science, Engi-
R-factor: however, the geometry looks reasonable, though neering and Technology for a studentship. J. F. G. thanks
with geometric data having rather high esds (s.u.’s). Better Dublin City University for the purchase of a Siemens P4
quality crystals of 1a were subsequently obtained via several diffractometer and computer system. Thanks to Dr D. Rai
recrystallization experiments and data were subsequently col- of the CSCB Mass Spectrometry Centre for mass analyses and

488 | New J. Chem., 2008, 32, 483–489 This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008
 View Article Online

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