Photochromic behavior of several new synthesized bis-1, 3-diazabicyclo[3.1.0]hex-3-enes

Article abstract of DOI:10.1002/poc.1550

Photochromic compounds (1-6) are synthesized and characterized and the results of their spectra are presented. The structure-photochromic behavior relationship (SPBR) of the synthesized compounds has been analyzed. Copyright

Full text of DOI:10.1002/poc.1550

Research Article
Received: 19 September 2008,
Revised: 10 February 2009,
Accepted: 24 February 2009,
Published online in Wiley InterScience: 2009
(www.interscience.wiley.com) DOI 10.1002/poc.1550
Photochromic behavior of several new
synthesized bis-1,3-diazabicyclo[3.1.0]hex-3-enes
a
a
a
a
*
H. Kiyani , N. O. Mahmoodi , K. Tabatabaeian and M. Zanjanchi
Photochromic compounds (1–6) are synthesized and characterized and the results of their spectra are presented.
The structure–photochromic behavior relationship (SPBR) of the synthesized compounds has been analyzed.
Copyright ß 2009 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: bis1,3-diazabicyclo[3,1,0]hex-3-ene; photochromic; structure–photochromic behavior relationship (SPBR)
and 6-(4-nitrophenyl)-2-phenyl-4,4-dipropyl-3,5-diazabicyclo[3,1,0]
hex-2-ene for detection of Sn (II) [8] and strontium (II) ions[9] at trace
levels in real samples, respectively.
INTRODUCTION
Photochromism is defined as light-induced reversible transform-
ation of a chemical species between two isomers having different
absorption spectra. The difference in geometry and electronic
structure between the two isomers, which is at the origin of the
color switch, has also been successfully exploited to reversibly
control other properties such as phase behavior of liquid crystals,
refractive index, fluorescence, redox potential, electron transfer,
and nonlinear optical properties. Although many types of
photochromic compounds have been reported so far, crystals
that show photochromic reactions in the crystal state are very
rare.[1–2] Recently, we became interested in the photochromism
and photoproduction of 1,3-diazabicyclo[3.1.0]hex-3-ene deriva-
tives with various substitution.[3–7] Colorless isomers A and B,
after remaining for ꢀ5–15 s under ordinary room light, changed
color; compound A with NO2 group in para position changed to
deep blue (A’ photoisomer) while compound B with NO2 group in
meta position changed to pink (B’ photoisomer) (Fig. 1). We
herein present 16 new photochromic compounds A, B (Fig. 1),
and 1–6 (Scheme 1). These molecules are new derivatives of this
well-known photochromic class 1,3-diazabicyclo[3.1.0]hex-3-ene.
Applications directly dependent upon the color change caused
by the molecular and electronic structures of the two (c ¼ close,
o ¼ open) (Fig. 1) or three species (cc, co, oo) (Scheme 4) and their
corresponding absorption or emission spectra include the
following: variable-transmission optical materials such as photo-
chromic ophthalmic lenses or camera filters; fluid flow
visualization; optical information storage; novelty items (toys,
T-shirts, etc.); authentication systems (security printing inks); and
cosmetics.
Solid-state organic photochromic molecules have attracted
much attention due to their potential applications in various
optoelectronic devices such as optical memory, optical switches,
electronic display, information storage, and so on. Typical
examples include N-salicylideneanilines, dinitrobenzylpyridines,
diphenylmaleonitriles, triarylimidazole dimers, aziridines, diary-
lethenes, diarylperfluorocyclopentenes, and biindenylidenedione
derivatives.[10–13] Among them, 1,3-diazabicyclo[3.1.0]hex-3-ene
derivatives synthesized from aziridine moiety are a class of
unique photochromic compounds, which generate bistable
molecules and undergo photochromism in the crystalline state.
This property allows us to consider bicyclic aziridines as possible
candidates in the search for radiochromic materials.
RESULTS AND DISCUSSION
Synthesis and photochromic investigations of novel
1,3-diazabicyclo[3.1.0]hex-3-enes
In continuation of prior work in the field of 1,3-diazabicyclo[3.1.0]
hex-3-ene systems and their applications in photochromism organic
chemistry,[14–16] we now present the synthesis and photochromic
investigations of novel bis-1,3-diazabicyclo[3.1.0]hex-3-enes. The
structures shown in this contribution possess a variety of functions
linked by aryl O-alkyl and O-benzyl spacers (Scheme 2).
Ketoaziridine 7 was prepared starting from chalcone, 8 to
9 at the double bond utilizing
facilitate dibrominated
bromine in chloroform solution, followed by aziridination with
solution of ammonia in absolute ethanol at room temperature
(Scheme 3).[3,5,7]
Requirements for photonics devices include: (1) thermal stability
of both isomers; (2) low fatigue can be cycled many times
without loss of performance, repeatable cycle number> 104;
(3) high sensitivity, quantum yield> 0.5; (4) rapid response;
(5) non-destructive readout capability; (6) reactivity in the solid
state. The more important requirements are thermal stability
of both isomers and fatigue resistant character. Recently, we
used novel potentiometric as membrane sensors based
on 6-(4-nitrophenyl)-2,4-diphenyl-3,5-diazabicyclo[3.1.0] hex-2-ene
*
Correspondence to: N. O. Mahmoodi, Department of Organic Chemistry,
University of Guilan, P.O. Box 1914, Rasht, Iran.
E-mail: mahmoodi@guilan.ac.ir
a
H. Kiyani, N. O. Mahmoodi, K. Tabatabaeian, M. Zanjanchi
Department of Organic Chemistry, University of Guilan, Rasht, Iran
J. Phys. Org. Chem. 2009, 22 559–567
Copyright ß 2009 John Wiley & Sons, Ltd.

H. KIYANI ET AL.
Figure 1. Absorption spectra of 6-(4-nitrophenyl)-2,4-diphenyl-2-(pyridin-2-yl)-1,3-diazabicyclo[3.1.0]hex-3-ene in EtOH (C ¼ 2.0 ꢁ 10ꢂ4 M) before and
after successive UV irradiation (lex 315 nm) A closed form (white) upon irradiation with 254 nm light to A0 open form (blue)
The merits of this system are based on (1) the synthesis of new
class of photochromic bicyclic aziridines; (2) the accessible
starting materials with prospective of industrial scale; (3) a facile
preparation with high percentage yield of products; and (4)
preparation of variety of symmetric photochromic bis-1,3-
diazabicyclo [3,1,0]hex-3-ene compounds.
These compounds can undergo reversible photocyclization
between their close–close ring isomer (cc), close–open ring
isomer (co), and open–open ring isomer (oo) under irradiation
using a light source of appropriate wavelength. Photoisomeriza-
tion of these photochromic compounds with a phenyl or arylen
bridging unit is illustrated in Scheme 4.
half-life reaction in cyclohexane, ethanol, acetone, and ethyl
acetate by irradiation with 254 nm UV light and visible light. Both
the cc-isomer (colorless) and the photogenerated isomer co- or
oo-form (colored) is stable at the ambient condition and the
coloration/decoloration cycles could be repeated without
destruction of the crystals. By increasing the duration of
irradiation, the population of the o-form in the colored crystals
increases, resulting in deepening of their color in the photo-
chromic crystals. The absorption spectra in the range of
200–800 nm (EtOH, C ¼ 2.0 ꢁ 10ꢂ4 M), as well as position of
absorption band maxima for the initial (lA nm), and photo-
induced (lB nm), were formed upon UV irradiation. The changes
in absorption of a bis1,3-diazabicyclo [3,1,0]hex-3-ene 1–6 in
ethanol at 254 nm are shown in Table 1.
All synthesized A, B, and 1–6 undergo reversible photochromic
reactions in a crystalline state during which a ring opening takes
place. We have also found that 1,3-diazabicyclo [3,1,0]hex-3-ene
systems undergo reversible photochromic reaction with a shorter
The open form of 1a after irradiation with UV-light absorbs at
longer wavelengths – lB
is red-shifted down to 261, 405 nm
max
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J. Phys. Org. Chem. 2009, 22 559–567

SPBR FOR THE SYNTHESIZED COMPOUNDS
Scheme 1.
Scheme 2. Synthetic route for the preparation of bis compounds 1–6
Scheme 3. Synthetic route for the preparation of aziridines
Scheme 4. Photochromic reactions of 1,3-diazabicyclo [3,1,0]hex-3-ene with phenylene or arylen linkage
J. Phys. Org. Chem. 2009, 22 559–567
Copyright ß 2009 John Wiley & Sons, Ltd.
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H. KIYANI ET AL.
Table 1. Spectra and lAmax, lBmax, lex, and percent yield of 1–6
Entry
lex, (nm)
lAmax, (nm)
207, 251
207, 244
298, 230, 248, 275
209, 251
lBmax, (nm)
Yield (%)
1a
1b
2a
2b
2c
2d
3a
3b
3c
3d
4a
4b
5
238
270
237
246
252
250
257
248
250
260
298
205, 227
—
284
207, 261, 405
207, 262, 360
258, 360, 406
212, 260, 412
205, 283, 376
220, 256, 320, 378
203, 280, 412
207, 269, 415
215, 280, 372
204, 283, 376
206, 406
82
76
80
85
65
85
74
75
74
71
77
69
74
55
205, 228
220, 246
203, 227, 259
207, 257
215, 228
206, 221
250, 280
205, 283, 374
208, 256
208, 245
406
208, 224, 264, 408
208, 264, 412
6
Figure 2. UV–Vis Absorption spectral changes of 3b and 3d (cc) upon irradiation under 254 nm light 3b0 and 3d0 (oo) in EtOH (C ¼ 2.0 ꢁ 10ꢂ4) before
and after successive UV irradiation (lex 248 and 260 nm), respectively
compared to the lA
originating at 207, 251 nm (Table 1). Both
tometer. Chemicals were purchased from Fluka, Merck, and
Aldrich. Melting points were uncorrected and determined by
Mettler Fp5 melting point apparatus. Products were character-
ized by 1H, 13C NMR, TLC, and mp). All NMR data were recorded in
CDCl3 using a Bruker Avance 500-MHz spectrometer. Chemical
shifts are reported in ppm (d) using deuterated solvents as
internal references.
Elemental analyses were made by a Carlo-Erba EA1110 CNNO-S
analyzer and agreed with the calculated values. Synthesis of
dialdehyde,[17–19] 4-nitrochalcone,[20] 2,3-dibromo-4-nitrochalcone,[5,7]
(3-(4-nitrophenyl)aziridin-2-yl)(phenyl) methanone 7a, and
(3-(3-nitrophenyl)aziridin-2-yl)(phenyl)methanone 7b were pre-
pared according to a standard procedure.[3]
max
compounds 1a and 1b exhibit acceptable light sensitivity. However,
1a shows a better photocoloration/photobleaching ratio.
The yield of preparation for compound 3b is more than 3d; the
open form of 3d absorbs at slightly shorter wavelengths – lBmax is
blue-shifted down to 376 nm compared to 3b lBmax 415 nm. Both
compound 3b and 3d exhibit acceptable light-sensitivity and
satisfactory photocoloration/photobleaching ratio. Compound
3b exhibits a higher light sensitivity than 3d (Fig. 2). The
pronounced photochromic behavior of 3b is attributed to the
presence of para-NO2 substitution effect. The 13C NMR of
compound 2c consists of a virtually pure mixture of (cc) and (oo)
in a ratio of ꢀ 66:34. This is best ascertained by monitoring the
total integral for five characteristic signals for (oo) and (cc) isomer.
The 1HNMR of 2c in the presence of even ordinary room light
indicates an interesting photoisomerization reaction and two sets
of signals for 2c (cc): 2c0 (oo) photoisomers with ratio of 66:34
could exist (Figs. 3 and 4).
6-(4-nitrophenyl)-2,4-diphenyl-2-(pyridin-3-yl)-
1,3-diazabicyclo[3.1.0]hex-3-ene (A): a typical procedure
(3-(4-nitrophenyl)aziridin-2-yl)(phenyl)methanone 7a (0.268 g,
1 mmol), NH4Br (0.1 g, 1 mmol), and the appropriate ketone
(1 mmol) were dissolved in 6 ml of absolute ethanol and stirred at
room temperature. Anhydrous gaseous ammonia was gently
blown into the reaction mixture for several hours. Alternatively,
instead of gaseous ammonia, 5 mmol NH4OOCCH3 was used. In
this case, the reaction was completed after 2–4 days instead of 1
week. A color change in the reaction mixture from white to blue
EXPERIMENTAL
The UV/Vis absorption spectra in the range 200–800 nm (EtOH,
C ¼ 2.10ꢂ4) as well as position of absorption band maxima for the
0
initial A (lAmax nm) and photoinduced A0 (lA max nm) photo-
isomers were measured with a Shimadzu UV-2100 spectropho-
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Copyright ß 2009 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2009, 22 559–567

SPBR FOR THE SYNTHESIZED COMPOUNDS
Figure 3. The 1HNMR and 13C NMR of 2c indicated mixture of two isomers (cc):(oo) in ratio ꢀ 66:34
Figure 4. 1HNMR of 2c indicated mixture of two photoisomers with ratio of 66:34 for 2c (cc): 2c’ (oo)
J. Phys. Org. Chem. 2009, 22 559–567
Copyright ß 2009 John Wiley & Sons, Ltd.
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H. KIYANI ET AL.
1
or greenish blue is characteristic for product formation. The
reaction mixture was filtered, washed with ethanol, dried in air,
and the resulting solid recovered, purified by silica gel column
chromatography and recrystallized by ethanol, methanol, or
some other suitable solvent. Collected as a white solid. Yield 85%,
mp 216–217 8C; closed-form, yield 85%, 1H NMR (500 MHz, CDCl3,
ppm): d 2.6 (s, 1H), 3.77 (s, 1H), 7.06 (m, 1H), 7.21 (t, J ¼ 8.3 Hz, 1H),
7.32 (t, J ¼ 7.6 Hz, 2H), 7.39–7.68 (m, 7H), 7.90 (d, J ¼ 7.9 Hz, 2H),
7.97 (d, J ¼ 7.90 Hz, 2H), 8.13 (d, J ¼ 8.36 Hz, 2H), 8.50 (d, J ¼ 4.4 Hz,
1H). After irradiation with UV light converted to blue (open-form,
15%, A0): 1H NMR (500 MHz, CDCl3, ppm): d 2.54 (s, 1H), 3.92 (s, 1H),
7.06 (m, 1H), 7.25 (t, J ¼ 7.7 Hz, 2H), 7.32 (t, J ¼ 7.6 Hz, 2H),
7.39–7.68 (m, 5H), 7.90 (d, J ¼ 7.9 Hz, 2H), 7.97 (d, J ¼ 7.90 Hz, 2H),
8.13 (d, J ¼ 8.36 Hz, 2H), 8.61 (d, J ¼ 4.4 Hz, 1H).
147.2, 169.9. Closed-form, meso, 50%, H NMR (500 MHz, CDCl3,
ppm): d 2.49 (s, 2H), 3.80 (s, 2H), 6.80 (s, 2H), 7.52–7.66 (m, 14H),
8.02 (d, J ¼ 7.4 Hz, 4H), 8.20 (d, J ¼ 7.5 Hz, 4H); 13C NMR (125 MHz,
CDCl3, ppm): d 41.4, 57.6, 96.9, 123.5, 127.0, 127.5, 128.5, 128.6,
128.8, 131.4, 131.7, 138.6, 145.7, 147.1, 170.4. Open-form, meso,
1
50%, H NMR (500 MHz, CDCl3, ppm): d 2.82 (s, 2H), 3.80 (s, 2H),
6.33 (s, 2H), 7.52–7.66 (m, 14H), 8.02 (d, J ¼ 7.4 Hz, 4H), 8.23 (d,
J ¼ 7.5 Hz, 4H); 13C NMR (125 MHz, CDCl3, ppm): d 47.4, 56.7, 95.7,
123.5, 127.1, 127.5, 128.5, 128.6, 128.8, 131.4, 131.7, 138.2, 145.7,
147.1, 169.5. Anal. Calcd for C38H28N6O4: C, 72.14; H, 4.46; N, 13.28;
found C, 72.17; H, 4.47; N, 13.29.
6-(3-nitrophenyl)-4-(4-(6-(3-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-3-en-2-yl)phenyl)-
2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene (1b; C38H28N6O4)
6-(3-nitrophenyl)-2,4-diphenyl-2-(pyridin-3-yl)-
1,3-diazabicyclo[3.1.0]hex-3-ene (B)
A similar procedure as applied for 1a was practical but instead of
7a same amount of 7b was utilized. Yield 76%, mp 203–204 8C,
white solid, IR (KBr, v/cmꢂ1): 3080, 3050, 1600, 1570, 1515, 1330,
1040, 1020, 835, 770, 740, 690. 1H NMR (500 MHz, CDCl3, ppm): d
2.57 (s, 2H), 3.80 (s, 2H), 6.85 (s, 2H), 7.52–7.75 (m, 14H), 7.92–8.00
(m, 4H), 8.12–8.14 (m, 2H), 8.25 (s, 2H); 13C NMR (125MHz, CDCl3,
ppm): d 41.4, 57.7, 95.9, 121.5, 122.5, 127.1, 128.6, 128.7, 128.9,
129.7, 131.7, 131.9, 140.4, 140.6, 140.7, 148.4, 170.7. After
irradiation with UV light converted to pink, open-form, 40%, dl, 1H
NMR (500 MHz, CDCl3, ppm): d 2.83 (s, 2H), 3.80 (s, 2H), 6.27 (s, 2H),
7.52–7.75 (m, 14H), 7.92–8.00 (m, 4H), 8.12–8.14 (m, 2H), 8.18 (s,
2H); 13C NMR (125MHz, CDCl3, ppm): d 47.6, 56.9, 97.3, 121.4,
121.5, 127.2, 128.6, 128.7, 128.9, 129.6, 131.7, 131.9, 140.4, 140.7,
A similar procedure as applied for A was practical but instead of
7a same amount of 7b was utilized. Yield 75%, mp 218–219 8C.
Closed-form, 90% 1H NMR (500 MHz, CDCl3, ppm): d 2.63 (d,
J ¼ 1.8 Hz, 1H), 3.78 (d, J ¼ 1.8 Hz, 1H), 7.06 (m, 1H), 7.20 (m, 1H),
7.32 (t, J ¼ 7.6 Hz, 2H), 7.40–7.48 (m, 4H), 7.55 (td, J ¼ 1.5, 7.9 Hz,
1H), 7.60 (t, J ¼ 7.7 Hz, 1H), 7.68 (d, J ¼ 7.7 Hz, 1H), 7.91 (d,
J ¼ 7.7 Hz, 2H), 8.07 (d, J ¼ 9.2 Hz, 2H), 8.09 (dd, J ¼ 1.0. 7.7 Hz, 1H),
8.17 (s, 1H), 8.52 (t, J ¼ 4.6 Hz, 1H). A white solid, after irradiation
with UV light converted to pinkish, (open-form, B0 10%) 1H NMR
(500 MHz, CDCl3): d 2.56 (d, J ¼ 1.9 Hz, 1H), 3.92 (d, J ¼ 1.9 Hz, 1H),
7.06 (m, 1H), 7.20 (m, 1H), 7.32 (t, J ¼ 7.6 Hz, 2H), 7.40–7.48 (m, 4H),
7.55 (td, J ¼ 1.5, 7.9 Hz, 1H), 7.60 (t, J ¼ 7.7 Hz, 1H), 7.73 (d,
J ¼ 7.7 Hz, 1H), 7.91 (d, J ¼ 7.7 Hz, 2H), 8.07 (d, J ¼ 9.2 Hz, 2H), 8.09
(dd, J ¼ 1.0. 7.7 Hz, 1H), 8.14 (s, 1H), 8.60 (d, J ¼ 4.6 Hz, 1H) ppm.
1
141.2, 148.4, 169.9. Closed-form, meso, 50%, H NMR (500 MHz,
CDCl3, ppm): d 2.54 (s, 2H), 3.80 (s, 2H), 6.80 (s, 2H), 7.52–7.75 (m,
14H), 7.92–8.00 (m, 4H), 8.12–8.14 (m, 2H), 8.25 (s, 2H); 13C NMR
(125MHz, CDCl3, ppm): d 41.3, 57.6, 95.8, 121.5, 122.6, 127.1, 128.6,
128.7, 128.9, 129.6, 131.5, 131.9, 138.8, 140.4, 140.7, 148.4, 170.8;
open-form, meso, 50%, 1H NMR (500 MHz, CDCl3, ppm): d 2.83 (s,
2H), 3.80 (s, 2H), 6.35 (s, 2H), 7.52–7.66 (m, 14H), 7.92–8.00 (m, 4H),
8.12–8.14 (m, 2H), 8.25 (s, 2H); 13C NMR (125MHz, CDCl3, ppm): d
47.5, 56.6, 97.2, 121.3, 121.5, 127.2, 127.6, 128.6, 128.7, 128.9,
131.6, 131.9, 138.4, 140.4, 140.7, 148.4, 169.8. Anal. Calcd for
C38H28N6O4: C, 72.14; H, 4.46; N, 13.28; found C, 72.16; H, 4.48; N,
13.28.
Preparation of 6-(4-nitrophenyl)-4-(4-(6-(4-nitrophenyl)-
4-phenyl-1,3-diazabicyclo[3.1.0] hex-3-en-
2-yl)phenyl)-2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene: a
typical procedure (1a; C38H28N6O4)
(3-(4-nitrophenyl)aziridin-2-yl)(phenyl)methanone 7a (0.536 g,
2 mmol), NH4Br (0.2 g, 2 mmol) and the appropriate aldehyde
(1 mmol) were dissolved in 10 ml of absolute ethanol and stirred
at room temperature. Anhydrous gaseous ammonia is gently
blown into reaction mixture for several hours. Alternatively,
instead of gaseous ammonia, 10 mmol NH4OOCCH3 was used. In
this case, the reaction was completed after 3 days instead of
2 weeks. A color was changed from orange into blue or greenish
blue for product formation. The reaction mixture was filtered,
washed with ethanol, dried in the air, and the resulting solid
recovered 0.72 g (yield 82%), mp 211–212 8C, white solid, purified
by silica gel column chromatography and recrystallized by
ethanol (65.5% yield), methanol, or some other suitable solvent.
(1a) IR (KBr, v/cmꢂ1): 3080, 3040, 1600, 1570, 1510, 1340, 1045,
1020, 860, 840, 770, 740, 690. Closed-form, dl, 60%, 1H NMR
(500 MHz, CDCl3, ppm): d 2.54 (s, 2H), 3.84 (s, 2H), 6.84 (s, 2H),
7.52–7.66 (m, 14H), 8.02 (d, J ¼ 7.4 Hz, 4H), 8.25 (d, J ¼ 7.0 Hz, 4H);
13C NMR (125MHz, CDCl3, ppm): d 41.5, 57.7, 96.9, 123.5, 127.6,
127.5, 128.5, 128.6, 128.8, 131.5, 131.7, 140.6, 145.8, 147.2, 170.5.
After irradiation with UV light converted to blue, open-form, 40%,
dl, 1H NMR (500 MHz, CDCl3, ppm): d 2.82 (s, 2H), 3.84 (s, 2H), 6.27
(s, 2H), 7.52–7.66 (m, 14H), 8.02 (d, J ¼ 7.4 Hz, 4H), 8.23 (d,
J ¼ 7.5 Hz, 4H); 13C NMR (125MHz, CDCl3, ppm): d 47.5, 56.7, 95.7,
123.5, 127.4, 127.5, 128.5, 128.6, 128.8, 131.5, 131.7, 141.0, 145.9,
Preparation of 4-(2-(4-(2-(6-(4-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-3-en-2-yl)-
phenoxy)butoxy)phenyl)-6-(4-nitrophenyl)-
2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene (2a; C48H40N6O6)
Synthesis of dialdehyde was completed according to the
standard procedure.[18–20] Yield 69%, mp 188–189 8C, beige
solid, IR (KBr, v/cmꢂ1): 3060, 3050, 2950, 2890, 1600, 1520, 1490,
1450, 1340, 1230, 1160, 1040, 1020, 860, 840, 758, 690.
Closed-form, 60%, 1H NMR (500 MHz, CDCl3, ppm):d 2.09–2.12
(m, 4H), 2.53 (s, 2H), 3.54 (s, 2H), 4.03–4.16 (m, 4H), 6.83–6.89 (m,
4H), 6.93 (s, 2H), 7.02 (d, J ¼ 8.8 Hz, 2H), 7.16–7.21 (m, 4H), 7.25 (d,
J ¼ 8.6 Hz, 4H), 7.37–7.43 (m, 8H), 7.93 (d, J ¼ 8.5 Hz, 4H), 8.03 (d,
J ¼ 8.4 Hz, 4H); after irradiation with UV light converted to blue
(open-form, 40%): 1H NMR (500 MHz, CDCl3, ppm): d 1.96–2.03 (m,
4H), 2.55 (s, 2H), 3.56 (s, 2H), 4.03–4.16 (m, 4H), 6.3 (s, 2H),
6.83–6.89 (m, 4H), 7.00 (d, J ¼ 7.5 Hz, 2H), 7.16–7.21 (m, 4H), 7.25
(d, J ¼ 8.6 Hz, 4H), 7.37–7.43 (m, 8H), 7.93 (d, J ¼ 8.5 Hz, 4H), 7.98
(d, J ¼ 8.5 Hz, 4H). Anal. Calcd for C48H40N6O6: C, 72.35; H, 5.06; N,
10.55; found C, 72.36; H, 5.08; N, 10.55.
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SPBR FOR THE SYNTHESIZED COMPOUNDS
Preparation of 4-(2-(5-(2-(6-(4-nitrophenyl)-
4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-en-
2-yl)phenoxy)pentyloxy)phenyl)-6-(4-nitrophenyl)-
2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene (2b, C49H42N6O6)
6.83 (s, 2H), 6.86 (d, J ¼ 6.6 Hz, 2H), 6.89 (t, J ¼ 5.6, 8.0 Hz, 2H), 7.08
(dd, J ¼ 1.4, 7.5 Hz, 2H), 7.24 (t, J ¼ 7.0 Hz, 2H), 7.33–7.37 (m, 2H),
7.43–7.52 (m, 8H), 7.96 (dd, J ¼ 1.2, 8.4 Hz, 4H), 8.00 (d, J ¼ 1.2 Hz,
2H), 8.09 (s, 2H); 13C NMR (125 MHz, CDCl3, ppm): d 26.6, 46.7, 57.1,
68.3, 91.9, 112.2, 120.4, 122.3, 122.5, 127.2, 128.8, 129.1, 129.2,
129.7, 129.9, 132.0, 132.2, 133.2, 141.2, 148.8, 157.0, 169.9. Anal.
Calcd for C48H40N6O6: C, 72.35; H, 5.06; N, 10.55; found C, 72.37; H,
5.07; N, 10.56.
Yield 85%, mp 172–173 8C, pinkish solid, after irradiation with UV
light converted to blue; IR (KBr, v/cmꢂ1): 3070, 3020, 2950, 2890,
1600, 1570, 1520, 1490, 1450, 1340, 1240, 1040, 1020, 740, 690.
Closed-form, 1H NMR (500 MHz, CDCl3, ppm):d 1.92 (t, J ¼ 5.0,
6.7 Hz, 2H), 1.97 (app d, J ¼ 5.0 Hz, 4H), 2.57 (s, 2H), 3.59 (s, 2H),
4.11 (q, J ¼ 5.6 Hz, 4H), 6.91 (q, J ¼ 7.4, 7.9 Hz, 4H), 6.97 (s, 2H), 7.07
(d, J ¼ 7.3 Hz, 2H), 7.25 (d, J ¼ 8.2 Hz, 4H), 7.29 (t, J ¼ 7.9 Hz, 2H),
7.44 (t, J ¼ 7.5 Hz, 4H), 7.52 (t, J ¼ 7.2 Hz, 2H), 7.85 (d, J ¼ 8.5 Hz,
4H), 7.81(d, J ¼ 7.5 Hz, 4H). 13C NMR (125MHz, CDCl3, ppm):d 23.9,
29.7, 40.7, 57.5, 68.7, 91.9, 11.8, 127.1, 120.5, 123.7, 123.8, 127.13,
127.7, 127.8, 128.3, 128.8, 129.0, 129.2, 130.1, 132.0, 146.3, 157.0,
170.2. Anal. Calcd for C49H42N6O6: C, 72.58; H, 5.22; N, 10.55; found
C, 72.60; H, 5.11; N, 10.56.
6-(4-nitrophenyl)-4-(4-(4-(4-(6-(4-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-3-en-2-yl)phenoxy)butoxy)-
phenyl)-2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene (3a,
C
48H40N6O6)
Yield 74%, mp 192–193 8C, beige solid. IR (KBr, v/cmꢂ1): 3080,
3030, 2950, 2890, 1600, 1510, 1450, 1340, 1242, 1105, 1045, 1020,
1
830, 770, 740, 695. Closed-form, 60%, H NMR (500 MHz, CDCl3,
ppm): d 1.96 (m, 4H), 2.49 (s, 2H), 3.73 (s, 2H), 3.99 (m, 4H), 6.73 (s,
2H), 6.85 (t, J ¼ 7.7 Hz, 4H), 7.38–7.40 (m, 6H), 7.48–7.53 (m, 8H),
7.96 (d, J ¼ 6.8 Hz, 4H), 8.14 (d, J ¼ 8.1 Hz, 2H); 13C NMR (125MHz,
CDCl3, ppm): d 26.4, 41.8, 58.2, 67.8, 96.2, 114.8, 124.0, 127.8,
128.4, 128.8, 128.9, 1293, 131.2, 132.1, 132.2, 147.7, 159.3, 170.7.
After irradiation with UV light converted to green (open-form,
40%) 1H NMR (500 MHz, CDCl3, ppm): d 1.96 (m, 4H), 2.75 (s, 2H),
3.73 (s, 2H), 3.99 (m, 4H), 6.20 (s, 2H), 6.92 (t, J ¼ 8.3 Hz, 4H),
7.38–7.40 (m, 6H), 7.48–7.53 (m, 8H), 7.96 (d, J ¼ 6.8 Hz, 4H), 8.20
(d, J ¼ 8.3 Hz, 2H). 13C NMR (125MHz, CDCl3, ppm): d 26.4, 48.4,
57.3, 67.9, 97.7, 115.0, 124.1, 127.7, 128.8, 128.9, 129.0, 129.3,
131.2, 131.9, 132.2, 145.9, 159.1, 169.9. Anal. Calcd for C48H40N6O6:
C, 72.35; H, 5.06; N, 10.55; found: C, 72.38; H, 5.07; N, 10.56.
6-(3-nitrophenyl)-4-(2-(6-(2-(6-(3-nitrophenyl)-
4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-en-
2-yl)phenoxy)hexyloxy)phenyl)-2-phenyl-
3,5-diazabicyclo[3.1.0]hex-2-ene (2c, C50H44N6O6)
As a white solid, yield 65%, mp 143–144 8C. IR (KBr, v/cmꢂ1): 3080,
3040, 2920, 2860, 1605, 1575, 1530, 1445, 1345, 1242, 1175, 1042,
1
1022, 830, 770, 735, 690. Closed-form, 66%, H NMR (500 MHz,
CDCl3, ppm): d 1.51–1.54 (qui, J ¼ 3.7, 7.4 Hz, 4H), 1.80 (t,
J ¼ 6.5 Hz, 4H) 2.53 (s, 2H), 3.74 (s, 2H), 3.94 (t, J ¼ 6.5 Hz, 4H), 6.74
(s, 2H), 6.85 (d, J ¼ 8.6 Hz, 2H), 7.40–7.56 (m, 14H), 7.97 (dt, J ¼ 1.6,
8.4 Hz, 4H), 8.10 (d, J ¼ 1.5 Hz, 2H), 8.21 (d, J ¼ 1.6 Hz, 2H); 13C NMR
(125MHz, CDCl3, ppm): d 26.3, 29.6, 41.5, 57.9, 68.2, 96.2, 114.8,
121.9, 122.8, 128.4, 128.9, 129.0, 129.2, 129.3, 129.7, 131.1, 132.1,
133.1, 140.8, 148.8, 159.1, 107.7. After irradiation with UV light
6-(4-nitrophenyl)-4-(4-(6-(4-(6-(4-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-3-en-2-yl)phenoxy)-
hexyloxy)phenyl)-2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene
(3b, C50H44N6O6)
1
converted to yellow color (open-form, 34%); H NMR (500 MHz,
CDCl3, ppm): d 1.51–1.54 (qui, J ¼ 3.7, 7.4 Hz, 4H), 1.80 (t,
J ¼ 6.5 Hz, 4H), 2.77 (d, J ¼ 1.5 Hz, 2H), 3.75 (d, J ¼ 2.0 Hz, 2H), 3.99
(t, J ¼ 6.6 Hz, 4H), 6.20 (d, J ¼ 2.0 Hz, 2H), 6.92 (d, J ¼ 6.9 Hz, 2H),
6.93 (t, J ¼ 6.7 Hz, 2H), 7.40–7.56 (m, 12H), 7.70 (d, J ¼ 7.7 Hz, 2H),
7.97 (dt, J ¼ 1.6, 7.0 Hz, 4H), 8.08 (s, 2H) 8.14 (dt, J ¼ 1.0, 2.0, 8.2 Hz,
2H). 13C NMR (125MHz, CDCl3, ppm): d 26.3, 29.6, 48.2, 56.9, 68.3,
97.7, 115.0, 122.9, 128.9, 129.8, 129.0, 129.2, 129.3, 131.9, 132.1,
133.0, 133.5, 148.9, 159.5, 169.9. Anal. Calcd for C50H44N6O6: C,
72.80; H, 5.38; N, 10.19; found C, 72.81; H, 5.40; N, 10.20.
Yield 75%, mp 167–169 8C, beige solid, IR (KBr, v/cmꢂ1): 3060,
3040, 2945, 2890, 1600, 1520, 1480, 1450, 1335, 1220, 1108, 1050,
1
865, 750, 745, 690. Closed-form, 73%, H NMR (500 MHz, CDCl3,
ppm): d 1.52 (app t, J ¼ 3.3, 7.0 Hz, 4H), 1.79 (d br, J ¼ 5.9 Hz, 4H)
2.50 (s, 2H), 3.74 (s, 2H), 3.93 (t, J ¼ 6.4 Hz, 4H), 6.74 (s, 2H), 6.84 (d,
J ¼ 8.3 Hz, 2H), 6.85 (d, J ¼ 8.2 Hz, 2H), 7.38–7.55 (m, 14H), 7.97 (d,
J ¼ 7.2 Hz, 4H), 8.14 (d, J ¼ 8.53 Hz, 2H); 13C NMR (125MHz, CDCl3,
ppm): d 26.3, 29.6, 41.8, 58.2, 68.2, 96.3, 114.8, 124.0, 127.8, 128.4,
128.8, 128.9, 129.3, 131.0, 132.0, 132.2, 146.0, 159.1, 170.0. After
irradiation with UV light converted to greenish blue (open-form,
27%): 1H NMR (500 MHz, CDCl3, ppm): d 1.52 (app t, J ¼ 3.3, 7.0 Hz,
4H), 1.79 (d br, J ¼ 5.9 Hz, 4H), 2.76 (s, 2H), 3.73 (s, 2H), 3.97 (t,
J ¼ 6.4 Hz, 4H), 6.20 (s, 2H), 6.92 (d, J ¼ 8.4 Hz, 2H), 6.93 (t,
J ¼ 8.4 Hz, 4H), 7.38–7.55 (m, 14H), 7.97 (d, J ¼ 7.15 Hz, 4H), 8.19 (d,
J ¼ 8.6 Hz, 4H); 13C NMR (125 MHz, CDCl3, ppm): d 26.3, 29.6, 48.4,
57.3, 68.3, 97.7, 115.0, 124.1, 127.7, 128.8, 129.0, 129.3, 129.3,
131.0, 131.9, 132.2, 147.7, 159.2, 169.9. Anal. Calcd for C50H44N6O6:
C, 72.80; H, 5.38; N, 10.19; found C, 72.82; H, 5.39; N, 10.21.
Preparation of 4-(2-(4-(2-(6-(3-nitrophenyl)-
4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-en-2-yl)phenoxy)-
butoxy)phenyl)-6-(3-nitrophenyl)-2-phenyl-3,5-
diazabicyclo[3.1.0]hex-2-ene (2d, C48H40N6O6)
Yield 85%, mp 172–173 8C, white solid. IR (KBr, v/cmꢂ1): 3080,
3020, 2950, 2890, 1600, 1570, 1510, 1450, 1340, 1240, 1045, 1022,
765, 740, 695. Closed-form, 34%, 1H NMR (500 MHz, CDCl3, ppm): d
2.22 (app t, J ¼ 6.6, 7.3 Hz, 4H), 2.60 (s, 2H), 3.59 (s, 2H), 4.18 (d,
J ¼ 3.1 Hz, 4H), 6.83 (s, 2H), 6.86 (d, J ¼ 6.6 Hz, 2H), 6.89 (t, J ¼ 5.6,
8.0 Hz, 2H), 7.05 (dd, J ¼ 1.3, 6.3 Hz, 2H), 7.24 (t, J ¼ 7.1 Hz, 2H),
7.33–7.37 (m, 2H), 7.43–7.52 (m, 8H), 7.96 (dd, J ¼ 1.2, 8.4 Hz, 4H),
8.01 (d, J ¼ 1.4 Hz, 2H), 8.08 (s, 2H); 13C NMR (125 MHz, CDCl3,
ppm): d 26.6, 40.5, 47.2, 68.4, 91.8, 112.1, 120.3, 122.2, 122.6, 127.1,
128.8, 128.9, 129.3, 129.7, 130.0, 132.0, 132.3, 133.3, 141.1, 148.6,
156.9, 170.2. After irradiation with UV light converted to pink
6-(3-nitrophenyl)-4-(4-(4-(4-(6-(3-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-3-en-2-
yl)phenoxy)butoxy)phenyl)-2-phenyl-3,5-
diazabicyclo[3.1.0]hex-2-ene (3c, C48H40N6O6)
Yield 74%, mp 139–140 8C, white solid. IR (KBr, v/cmꢂ1): 3080,
3020, 2940, 2880, 1605, 1520, 1510, 1345, 1245, 1170, 1045, 1020,
1
(open-form, 66%) H NMR (500 MHz, CDCl3, ppm): d 2.12 (app t,
1
J ¼ 4.9, 6.8 Hz, 4H), 2.63 (s, 2H), 3.61 (s, 2H), 4.14 (d, J ¼ 5.7 Hz, 4H),
830, 770, 735, 690. Closed-form, 58%, H NMR (500 MHz, CDCl3,
J. Phys. Org. Chem. 2009, 22 559–567
Copyright ß 2009 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/poc

H. KIYANI ET AL.
ppm): d 1.95 (qui, J ¼ 3.3, 6.4 Hz, 4H), 2.52 (d, J ¼ 3.0 Hz, 2H), 3.74 (s,
2H), 4.02 (t, J ¼ 7.0 Hz, 4H), 6.73 (d, J ¼ 3.0 Hz, 2H), 6.86 (t,
J ¼ 8.7 Hz, 4H), 7.40–7.56 (m, 14H), 7.98 (d, J ¼ 7.5 Hz, 4H), 8.10 (d,
J ¼ 2.0 Hz, 4H), 8.21 (s, 2H); 13C NMR (125 MHz, CDCl3, ppm): d 26.4,
41.5, 57.9, 67.9, 96.2, 114.8, 115.0, 122.0, 122.8, 128.9, 129.0, 129.3,
129.7, 131.2, 132.1, 133.0, 133.7, 140.8, 148.8, 159.0, 170.8. After
irradiation with UV light converted to yellow (open-form, 42%): 1H
NMR (500 MHz, CDCl3, ppm): d 1.95 (qui, J ¼ 3.3, 6.4Hz, 4H), 2.77 (s,
2H), 3.74 (s, 2H), 4.05 (t, J ¼ 7.2 Hz, 4H), 6.20 (d, J ¼ 3.0 Hz, 2H), 6.93
(t, J ¼ 8.7 Hz, 4H), 7.40–7.56 (m, 12H), 7.70 (d, J ¼ 7.6 Hz, 4H), 7.98
(d, J ¼ 7.5 Hz, 4H), 8.08 (s, 2H), 8.13 (d, J ¼ 8.1 Hz, 2H); 13C NMR
(125 MHz, CDCl3, ppm): d 26.4, 48.2, 56.9, 68.0, 97.7, 114.9, 115.1,
122.0, 123.0, 128.5, 129.0, 129.1, 129.3, 129.8, 131.2, 132.1, 133.1,
133.7, 140.0, 148.9, 159.4, 169.9. Anal. Calcd for C48H40N6O6: C,
72.35; H, 5.06; N, 10.55, found C, 72.36; H, 5.08; N, 10.06.
158.7, 170.0. Anal. Calcd for C52H40N6O6: C, 73.92; H, 4.77; N, 9.95;
found C, 73.95; H, 4.78; N, 9.97.
4-(4-(4-((4-(6-(3-nitrophenyl)-4-phenyl-1,3-diazabicyclo-
[3.1.0]hex-3-en-2-yl)phenoxy) methyl)benzyloxy)phenyl)-
6-(3-nitrophenyl)-2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene
(4b, C52H40N6O6)
Yield 69%, white solid, mp 169–170 8C; IR (KBr, v/cmꢂ1): 3070,
3050, 2960, 1605, 1580, 1515, 1440, 1345, 1230, 1170, 1040, 1020,
770, 740, 690. Closed-form, 50%, 1H NMR (500 MHz, CDCl3, ppm): d
2.53 (s, 2H), 3.75 (s, 2H), 5.05 (d, J ¼ 5.0 Hz, 4H), 6.75 (s, 2H),
6.93–6.95 (dq, J ¼ 3.7, 8.6 Hz, 4H), 7.42–7.54 (m, 16H), 7.56 (d,
J ¼ 7.6 Hz, 2H), 7.98 (d, J ¼ 7.4 Hz, 4H), 8.10 (dt, J ¼ 3.9, 8.1 Hz, 2H),
8.22 (s, 2H); 13C NMR (125 MHz, CDCl3, ppm): d 41.6, 57.9, 70.1,
96.2, 115.2, 121.9, 122.8, 128.1, 128.9, 129.0, 129.2, 129.7, 131.6,
132.2, 133.1, 134.0, 137.1, 140.8, 148.8, 158.7, 170.8. After
irradiation with UV light converted to yellow, (open-form, 50%) 1H
NMR (500 MHz, CDCl3, ppm): d 2.77 (s, 2H), 3.75 (s, 2H), 5.08 (d,
J ¼ 5.0 Hz, 4H), 6.21 (s, 2H), 6.99–7.02 (dq, J ¼ 3.7, 8.6 Hz, 4H),
7.42–7.54 (m, 16H), 7.71 (d, J ¼ 7.6 Hz, 2H), 7.98 (d, J ¼ 7.4 Hz, 4H),
8.09 (s, 2H), 8.14 (app dt, J ¼ 8.2 Hz, 2H); 13C NMR (125 MHz, CDCl3,
ppm): d 48.2, 56.9, 70.2, 97.7, 115.4, 121.9, 123.0, 128.0, 128.5,
128.9, 129.0, 129.3, 129.7, 131.9, 132.1, 133.0, 134.0, 137.2, 140.8,
148.9, 159.2, 170.0. Anal. Calcd for C52H40N6O6: C, 73.92; H, 4.77; N,
9.95; found C, 73.93; H, 4.77; N, 9.96.
6-(3-nitrophenyl)-4-(4-(6-(4-(6-(3-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-3-en-2-yl)phenoxy)-
hexyloxy)phenyl)-2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene
(3d, C50H44N6O6)
Yield 71%, mp 170–171 8C, white solid; IR (KBr, v/cmꢂ1): 3060,
3030, 2950, 2900, 1600, 1518, 1482, 1450, 1340, 1220, 1105, 1040,
1
860, 750, 740, 690. Closed-form, 70%, H NMR (500 MHz, CDCl3,
ppm): d 1.52 (m, 4H), 1.78 (m, 4H) 2.52 (s, 2H), 3.73 (s, 2H), 3.93 (t,
J ¼ 6.4 Hz, 4H), 6.74 (s, 2H), 6.85 (t, J ¼ 6.6, 8.2 Hz, 2H), 7.39–7.45
(m, H), 7.45–7.55 (m, H), 7.97 (d, J ¼ 7.2 Hz, 4H), 8.10 (s, 4H), 8.22 (s,
2H); 13C NMR (125MHz, CDCl3, ppm): d 26.3, 29.6, 41.5, 57.9, 68.2,
96.3, 114.8, 121.9, 128.4, 128.5, 128.9, 129.0, 129.3, 129.7, 131.1,
132.1, 133.1, 140.8, 148.8, 159.1, 170.7. After irradiation with UV
4-(3-(4-((3-(6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo-
[3.1.0]hex-3-en-2-yl)phenoxy)-
methyl)benzyloxy)phenyl)-6-(4-nitrophenyl)-
2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene (5, C52H40N6O6)
1
light converted to yellow (open-form, 30%) H NMR (500 MHz,
Yield 74%, mp 144–145 8C, pinkish solid; IR (KBr, v/cmꢂ1): 3060,
3030, 2930, 2890, 1600, 1520, 1495, 1450, 1340, 1220, 1050, 1010,
CDCl3, ppm): d 1.52 (m, 4H), 1.79 (m, 4H), 2.77 (s, 2H), 3.73 (s, 2H),
3.98 (t, J ¼ 6.5, 7.0 Hz, 4H), 6.20 (s, 2H), 6.92 (t, J ¼ 6.6, 8.2 Hz, 2H),
6.93 (t, J ¼ 8.4 Hz, 4H), 7.39–7.45 (m, H), 7.45–7.55 (m, H), 7.70 (d,
J ¼ 7.4 Hz, 2H), 7.97 (d, J ¼ 7.2 Hz, 4H), 8.08(s, 2H), 8.14 (d,
J ¼ 7.8 Hz, 2H); 13C NMR (125 MHz, CDCl3, ppm): d 26.3, 29.6, 48.2,
56.9, 68.3, 115.0, 121.9, 122.8, 128.4, 128.5, 128.9, 129.0, 129.3,
129.8, 131.0, 132.1, 133.0, 140.9, 148.9, 159.1, 169.9. Anal. Calcd for
C50H44N6O6: C, 72.80; H, 5.38; N, 10.19, found C, 72.82; H, 5.39; N,
10.21.
1
860, 835, 750, 690. Closed-form, 58%, H NMR (500 MHz, CDCl3,
ppm): d 2.47 (s, 2H), 3.73 (s, 2H), 5.01 (d, J ¼ 5.6 Hz, 4H), 6.75 (s, 2H),
6.89 (dd, J ¼ 2.1, 6.1 Hz, 2H), 7.11–7.18 (m, 4H), 7.24 (t, J ¼ 3.9 Hz,
4H), 7.47 (d, J ¼ 7.2 Hz, 4H), 7.53 (d, J ¼ 8.1 Hz, 4H), 7.96 (t,
J ¼ 7.4 Hz, 4H), 8.14 (dd, J ¼ 3.5, 8.5Hz, 4H); 13C NMR (125MHz,
CDCl3, ppm): d 42.0, 58.1, 70.1, 96.4, 114.1, 114.8, 120.4, 124.1,
127.7, 128.2, 128.9, 129.3, 130.1, 131.9, 132.1, 137.1, 140.6,
147.9,159.2, 170.9. After irradiation with UV light converted to
green (open-form, 42%): 1H NMR (500 MHz, CDCl3, ppm): d 2.77 (s,
2H), 3.71 (d, J ¼ 2.3 Hz, 2H), 5.08 (d, J ¼ 5.6 Hz, 4H), 6.21 (d,
J ¼ 2.3 Hz, H), 6.94 (dd, J ¼ 2.1, 6.2 Hz, 2H), 7.11–7.18 (m, 4H), 7.33
(t, J ¼ 8.2 Hz, 4H), 7.48 (d, J ¼ 7.3 Hz, 4H), 7.53 (d, J ¼ 8.1 Hz, 4H),
7.96 (t, J ¼ 7.5 Hz, 4H), 8.20 (d, J ¼ 8.6 Hz, 4H); 13C NMR (125 MHz,
CDCl3, ppm): d 48.3, 57.3, 70.2, 97.8, 114.1, 114.8, 119.9, 124.1,
127.7, 128.1, 129.0, 129.3, 130.1, 131.8, 132.3, 137.2, 142.8, 145.9,
159.4, 170.3. Anal. Calcd for C52H40N6O6: C, 73.92; H, 4.77; N, 9.95;
found C, 73.95; H, 4.78; N, 9.97.
4-(4-(4-((4-(6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo-
[3.1.0]hex-3-en-2-yl)phenoxy) methyl)benzyloxy)phenyl)-
6-(4-nitrophenyl)-2-phenyl-3,5-diazabicyclo[3.1.0]hex-2-ene
(4a,C52H40N6O6)
Yield 77%, white solid, mp 165–166 8C; IR (KBr, v/cmꢂ1): 3080,
3050, 2980, 1600, 1580, 1510, 1445, 1350, 1240, 1170, 1110, 1040,
1
1020, 770, 740, 690. Closed-form, 60% H NMR (500 MHz, CDCl3,
ppm): d 2.50 (s, 2H), 3.75 (s, 2H), 5.05 (d, J ¼ 4.3 Hz, 4H), 6.74 (s, 2H),
6.93–6.95 (q, J ¼ 3.5, 8.6 Hz, 4H), 7.39–7.46 (m, 10H), 7.50 (t,
J ¼ 7.4 Hz, 4H), 7.53–7.56 (m, 4H), 7.97 (d, J ¼ 7.1 Hz, 4H), 8.14 (d,
J ¼ 8.1 Hz, 4H); 13C NMR (125 MHz, CDCl3, ppm): d 41.8, 58.2, 70.1,
96.2, 115.2, 124.0, 127.8, 128.3, 128.8, 129.0, 129.2, 131.6, 132.2,
146.0, 147.7, 158.7, 170.7. After irradiation with UV light converted
to blue (open-form, 40%) 1H NMR (500 MHz, CDCl3, ppm): d 2.76 (s,
2H), 3.73 (s ¼ 2H), 5.09 (d, J ¼ 4.1 Hz, 4H), 6.20 (s, 2H), 6.99–7.02 (q,
J ¼ 3.5, 8.6 Hz, 4H), 7.39–7.46 (m, 10H), 7.50 (t, J ¼ 7.4 Hz, 4H),
7.53–7.56 (m, 4H), 7.97 (d, J ¼ 7.1 Hz, 4H), 8.20 (d, J ¼ 8.7 Hz, 4H).
13C NMR (125 MHz, CDCl3, ppm): d 48.4, 57.3, 70.1, 97.7, 115.4,
124.1, 127.8, 128.1, 128.5, 128.8, 129.0, 131.9, 132.1, 146.0, 147.8,
6-(4-nitrophenyl)-4-(2-((4-((2-(6-(4-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-3-en-2-yl)phenoxy)-
methyl)phenyl)methoxy)phenyl)-2-phenyl-3,5-
diazabicyclo[3.1.0]hex-2-ene (6), C52H40N6O6)
Yield 70%, mp 186–187 8C, beige solid; IR (KBr, v/cmꢂ1): 3080,
3040, 2940, 2890, 1600, 1518, 1495, 1450, 1340, 1220, 1040, 1020,
1
860, 840, 750, 690. Closed-form, 55%, H NMR (500 MHz, CDCl3,
ppm): d 2.63 (s, 2H), 3.69 (s, 2H), 5.20 (s, 4H), 6.88–6.93 (m, 40H),
7.02 (s, 2H), 7.13 (t, J ¼ 6.3 Hz, 2H), 7.30–7.33 (m, 4H), 7.39 (d,
J ¼ 6.2 Hz, 4H), 7.43–7.42 (m, H), 8.01 (d, J ¼ 6.9 Hz, 4H), 8.05 (d,
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Copyright ß 2009 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2009, 22 559–567

SPBR FOR THE SYNTHESIZED COMPOUNDS
J ¼ 8.7 Hz, 4H). After irradiation with UV light converted to blue
(open-form, 45%): 1H NMR (500 MHz, CDCl3, ppm): d 2.62 (s, 2H),
3.61 (s, 2H), 5.17 (s, 4H), 6.60 (s, 2H), 6.98–7.00 (m, 4H), 7.13 (t,
J ¼ 6.3 Hz, 2H), 7.30–7.33 (m, 4H), 7.36 (d, J ¼ 5.8 Hz, 4H), 7.43–7.42
(m, H), 7.92 (d, J ¼ 5.3 Hz, 4H), 8.01 (d, J ¼ 6.9 Hz, 4H), 8.14 (d,
J ¼ 5.4 Hz, 4H). Anal. Calcd for C52H40N6O6: C, 73.92; H, 4.77; N,
9.95; found C, 73.94; H, 4.77; N, 9.97.
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J. Phys. Org. Chem. 2009, 22 559–567
Copyright ß 2009 John Wiley & Sons, Ltd.
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