Chemical Physics 237 1998.

425442

Complexes of spiropyran-derived merocyanines with metal ions:

relaxation kinetics, photochemistry and solvent effects
Alexander K. Chibisov 1, Helmut Gorner

Max-Planck-Institut fur
an der Ruhr, Germany
Strahlenchemie, D-45413 Mulheim

Received 20 May 1998

Abstract
The complexation of spiropyran-derived merocyanines having a 6-nitro group in the pyran moiety 6-NO 2-BIPSs. or no
nitro group and certain transition or rare-earth metal ions M nq, n s 2, 3. were studied by steady-state and time-resolved
techniques in acetonitrile, butyronitrile, acetone and dioxane at room temperature. The overall kinetics of complex formation
are governed by equilibria between the spiropyran Sp., trans-merocyanine trans. and complex trans-M nq . forms. For this
two-step system two relaxation times are experimentally accessible which refer to fast t I . and slow t II . relaxation kinetics.
Thermal or photochemical perturbation of the equilibria leads to the same t II value for a given 6-NO 2-BIPS and metal ion
in defined concentrations. With increasing wM nq x, t II strongly increases and finally approaches the time needed for the
thermal Sp trans conversion. Water in small concentration - 0.3 M., which is necessary for dissolving the salt, does not
affect the properties of complexes significantly, but above 1 M the complex concentration decreases steeply. The
photophysical processes of complexes with 6-NO 2-BIPSs are weak fluorescence and mainly radiationless decay of the
excited singlet state, whereas intersystem crossing plays a role mainly for Pb II and intramolecular energy transfer mainly for
Co II or Ni II. Photochemical reactions are trans cis photoisomerization via the triplet state Pb II . and photosubstitution of
the trans isomer by a solvent as another ligand via the singlet state with spiropyran ring closure., e.g. for MnII or ZnII.
q 1998 Elsevier Science B.V. All rights reserved.

1. Introduction
During the last decade photochromism has gained much renewed attention mainly due to many promising
applications, e.g. switching devices for 3-dimensional optical memory w1,2x, display and communication systems
w3x, photoregulation of various physical and chemical properties of polymers w4x, signal transducer receptors w5x,
adaptive filter for optical image processing w6x and ophthalmic lenses w7x. Among the variety of photochromic
compounds, spiropyrans, spiroxazines, chromenes, fulgides, and some others w8,9x are the subject of keen
interest.

)
1

Corresponding author. E-mail: goerner@mpi-muelheim.mpg.de

On leave from the Center of Photochemistry, Russian Academy of Sciences, 117421 Moscow, Russia.

0301-0104r98r$ - see front matter q 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 1 - 0 1 0 4 9 8 . 0 0 2 9 1 - 2

426

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

The photochemistry of spiropyrans BIPSs., especially of 6-NO 2-substituted derivatives 6-NO 2-BIPSs. is
well documented w1032x. Essential features are the involvement of the triplet state in CO bond cleavage,
subsequent colouration due to formation of a merocyanine-type trans isomer open form. and formation of a cis
isomer as short-lived intermediate in photocolouration w2832x. Due to photochemical CO bond cleavage, four
trans conformers with the central transoid segment can be produced where the structure of the most stable one is
a matter of controversy w21,26,33,34x. A peculiar property of spiropyrans is the enhancement of colouration
upon UV irradiation. After removal of light, the colour of the spiropyran reaches its original value within a time
which depends essentially on temperature w1013x. One reason for the limited application potential of
spiropyran photochromism is its low fatigue resistance w35,36x. Spiroxazines appear, to some extent, to be free
from this disadvantage w37,38x, although their spectroscopic properties are not strongly influenced by changes in
structure. Thus, new approaches are required to satisfy the growing demands for modern applications.
Spiropyrans, in particular 6-NO 2-8-OMe-BIPSs, form complexes with certain d- and f-elements in solution
w3949x. While the colour of a spiropyran in polar solvents originates from absorption of its merocyanine-type
trans isomer, a marked blue shift is caused by complexation with two oxygen atoms of the trans isomer of
8-OMe-BIPS derivatives. The type of metal ion only slightly influences the spectral properties of the complexes,
in contrast to the relaxation time which can differ by one order of magnitude w4346x. For complexes with Co II ,
Ni II and CuII , one may also expect an increase in fatigue resistance for spiro compounds from efficient excited
state quenching due to intramolecular energy transfer to the lower positioned energy levels of the metal ions.
Thus, complexation provides a possibility to influence the photochromic properties of spiro compounds and
requires further study to elucidate the mechanism of complexation.
In this paper the studies of complexes of BIPSs with metal ions are extended. The 6-NO 2-BIPSs
1X-RX-3X ,3X-dimethyl-6-nitro-8-R-spirow2 H-1-benzopyran-2,2X-indolinex. system provides the possibility of examining the primary steps in complexation. We aim at a deeper insight into the relaxation kinetics and the
photophysical and photochemical properties of the complexes of spiropyran-derived merocyanines with Mg II ,
Pb II , transition and rare-earth metal nitrates. The relaxation kinetics and photoprocesses are linked in several
aspects because knowledge of the ground state equilibria is a prerequisite for the deactivation pathways and
photosubstitution is a feedback.

2. Experimental
The spirow2 H-1-benzopyran-2,2X-indolinex derivatives 17 have been synthesized according to methods
described elsewhere w50,51x. The solutions of complexes were prepared by addition of metal nitrates typical
concentration: 30 mM., which were dissolved in neat water prior to mixing, to a given spiropyran in dioxane,
acetone, butyronitrile or acetonitrile. All concentrations of metal nitrates refer to the initial values. The solvents
Merck. which were of purest quality commercially available Uvasol. or purified by distillation 1,4-dioxane
and butyronitrile. and the nitrates were used as supplied. The absorption spectra and relaxation kinetics were

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

427

measured on a spectrophotometer PerkinElmer 554. prior to or after continuous irradiation at 313, 366, 436 or
f 500 nm with a 1000 W XeHg lamp and a monochromator. The fluorescence spectra were recorded on
spectrofluorimeters SpexFluorolog and PerkinElmer LS-5.. The quantum yield was determined using cresyl
violet in ethanol F f s 0.54 at 258C, lexc s 500530 nm. as reference with optically matched samples having
absorbances of 0.3 at lexc . The transient absorption measurements were carried out using the second or third
harmonic from a Nd:YAG laser JK Lasers, system 2000., lexc s 530 or 354 nm, respectively, or the 308 nm
output from an excimer laser Lambda Physik, EMG 200.. The laser set-up was essentially the same as
described previously w30,49x. The measurements refer to ca. 248C.

3. Results and discussion

3.1. Ground state spiropyrantrans-merocyanine complex equilibria
The properties of 6-NO 2-BIPS derivatives in solution are determined by the ground state equilibrium 1.
between the Sp form and the trans-merocyanine w2832x.

1.

Here, the rate constants for equilibrium 1. are k 1 and ky1 and the equilibrium constant is K 1 s k 1rky1. The
absorption spectrum has two bands, e.g. that of 3 in acetonitrile has maxima at lSp s 356 nm and l t s 580 nm,
referring to the Sp and trans form, respectively Fig. 1a.. The molar absorption coefficients of the 6-NO 2-BIPSs

Fig. 1. Absorption spectra in acetonitrile for a. 3 in the absence of additives - - -. and in the presence of 30 mM - -. and 70 mM .
Nd III and b. 7 for wNd III x s 0.1 mM; inset: absorption changes at 480 upon and after irradiation at 313 upper. and 436 lower. nm.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

428

at lSp s 335355 nm and lt are Sp s 0.81.0. = 10 4 My1 cmy1 and t f 4 = 10 4 My1 cmy1 , respectively
w27,49x. K 1 is estimated using A trA Sp , the ratio of absorbances at lt and lSp and the ratio of the absorption
coefficients, Sp r t f 0.25. For all cases examined, A trA Sp is relatively small Table 1..
Formation of complexes of 6-NO 2-BIPSs with metal nitrates in solvents of medium or higher polarity is
accompanied by a major broad absorption band in the visible range maximum: lcom .. A typical case is shown
in Fig. 1a for 3 in acetonitrile in the presence of Nd III , lcom s 485 nm. The l com values are slightly specific for
a given metal nitrate and rather independent of the choice of the 6-NO 2-BIPSs Table 2. and, to a certain extent,
of solvent not shown.. Only for CuII in acetonitrile, but not in acetone w49x, is lcom further blue-shifted. For 6
and 7 Fig. 1b., where almost no colouration occurs in the absence of metal ions w30x, complexation also occurs
in the presence of Nd III.
The observed complex trans-M nq . is suggested to be due to coupled equilibria 1. and 2., where
K 2 s k 2rky2 .

2.

Here, S is the organic solvent and m the number of molecules coordinated on the metal ion. The equilibrium
between trans-M nq and the Sp form is described by A com rA Sp , the ratio of absorbances at the two maxima,
lcom and lSp . For a sufficiently large M nq concentration ) 10 mM., the A com rA Sp ratio, as a measure of the

Table 1
Absorption maximum, ratio of absorbances in the VIS versus UV and relaxation times of the trans isomer and its complex a
Compound

Solvent

lt
nm.

A t r A Sp

b
1rky1
s.

1rk 1c
s.

t dII
s.

acetone
acetonitrile
acetone
butyronitrile
acetonitrile
dioxane
acetone
butyronitrile
acetonitrile
acetone
acetonitrile
acetone
acetonitrile
acetonitrile
acetonitrile

565
562
598
595
595
600
580
578
580
594
583
605
595

0.03
0.01
0.12
0.12
0.26
0.02
0.06
0.07
0.12
0.06
0.15
0.01
0.02
- 0.01
- 0.01

80
160e
60

1=10 4
6=10 4
2000

810
1500
510

4
5
6
7
a

50
30
25
35
35
15
20
12
15

In air-saturated solution; wSpx s 0.10.5 mM; values for acetone are taken from Ref. w49x.
t t Sp , following irradiation at 366 nm.
c
Calculated from K 1.
d
Calculated for wM nq x s 0.10 mM and K 2 s1=10 5 My1.
e
Using lexc s 308 nm.
b

770
6000
1700
1750
1200
1000
500
4800
3000

330
310
240
320
300
140
160
130
160

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

429

Table 2
Absorption maximum, ratio of absorbances in the VIS versus UV and slow relaxation time of the complex a
Compound
1
2
3

5
6
7

M nq
III

Nd
Nd III
Mg II
MnII
Co II
Ni II
CuII
ZnII
Cd II
Pb II
Y III
Pr III
Nd III
EuIII
Tb III
LaIII
Mg II
Ni II
ZnII
Pb II
Nd III
Nd III
Nd III
Nd III

lcom nm.

A com r A Sp

485
492
490
492
485
490
360
468
495
478
470
478
485
474
470
475
490
475
468
478
485
520
520
460

0.03
0.9
0.2
0.4
0.5
0.06
c
0.8
0.3
0.7
0.7
1.6
1.6
1.5
1.45
1.0
0.3
0.3
0.9
0.7
1.64
- 0.03
0.3
0.6

t IIb s.
260
100
160
250
40
360
150
300
450
700
600
600
600
500
150
200
400
300
600
50
1200
1500

In air-saturated acetonitrile; wSpx s 0.080.12 mM and wM nq x s 0.10 mM.

Either thermally upon metal nitrate addition, t Sp com ., or after irradiation at 313 nm for wM nq x - 0.2 mM. or 436 nm tcom Sp ..
c
Different complex than in the other cases.

complex concentration, is generally significantly larger than the A trA Sp ratio. A com rA Sp increases with the
M nq concentration, the curve is linear at low values and levels off at higher Fig. 2a.. From equilibria 1. and
2. it follows that the complex concentration for wM nq x o 4 wtrans-M nq xe is given by:

w trans-M nq x e
K 1 K 2 w M nq x o
s
.
w Sp x o
1 q K 1 q K 1 K 2 w M nq x o

3a .

Here, subscripts e and o refer to equilibrium conditions and initial values, respectively. The A com rA Sp
values for a fixed wM nq x of 0.10 mM, ranging from 0.06 for 3rNi II in acetonitrile to 1.6 for Nd III , are compiled
in Table 2. When the molar absorption coefficient is taken independently of the type of the metal ion, this
variation is proportional to K 2 . From A com rA Sp s 1.0 for 3 and wNd III x s 40 mM the wtrans-M nq xerwSpx o ratio
is 0.33 using com s 3 = 10 4 My1 cmy1 . w49x and with K 1 s 0.03 it follows that K 2 s 2.5 = 10 5 My1. The
curves for 3 in acetonitrile in Fig. 2a refer to K 2 s 3 = 10 5, 1 = 10 5 and 3 = 10 4 My1 for Nd III , Pb II and Mg II ,
respectively.
3.2. Thermally actiated slow relaxation kinetics
Addition of M nq in a low concentration causes a small and relatively fast increase of A 480 . These build-up
kinetics at 480 nm are first-order processes and define a relaxation time t Sp com . of complex formation. For a
fixed M nq concentration of 0.1 mM t Sp com was determined from plots of the linear dependences versus time
of log A m y A.r A m y A 0 ., where A 0 and A m denote the initial and final max. values, respectively, cf. w49x.

430

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

Fig. 2. Plots versus metal ion concentration of a. absorption of the complex and b. relaxation time for 3 0.1 mM. in acetonitrile using
Mg II ^., Pb II `. and Nd III e.; the lines were calculated using K 2 s 3=10 5, 1=10 5 and 3=10 4 My1 and Eqs. 3a. and 3b. for a.
and b., respectively.

Plots of t Sp com versus log wM nq x are shown in Fig. 3. Significantly larger A com rA Sp and t Sp com values were
obtained for wM nq x s 1 mM Table 2. and similar effects were observed for 4 in contrast to 5, where bidentate
complexes are practically not formed.
The overall kinetics of complex formation are also governed by equilibria 1. and 2.. For this two-step
system the conversion of Sp into trans-M nq occurs via the trans form as steady-state intermediate. For
wM nq x 4 wtransx using steady-state approximation, the relaxation time is given by:

1rky2 . q 1rky1 . K 2 w M nq x o
t Sp - com s
.
1 q K 1 K 2 w M nq x o

3b .

The curves in Fig. 2b for 3 in acetonitrile in the presence of Nd III , Pb II and Mg II refer to K 2 s 3 = 10 5, 1 = 10 5
and 3 = 10 4 My1 , respectively.

Fig. 3. Dependence of the relaxation time versus log wM nq x for 3 0.1 mM. in acetonitrile for Mg II ^,'., Pb II `,v . and Nd III e,l. as
experimental results; the lines were calculated using Eq. 3b. and K 2 s 3=10 5 1., 1=10 5 2. and 3=10 4 3. My1 ; t Sp com ',v,l .
tcom Sp ^,`,e..

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431

When water is added to the 3rNd IIIracetonitrile mixture, the absorption band at 480 nm decreases and a new
band appears at 540 nm Fig. 4a. which originates from the non-complexed trans isomer in the more polar
mixture containing a surplus of water.

4.

On the other hand, addition of water to 3 in acetonitrile not shown. causes a blue-shift of l t from 580 to 540
nm for 10% water and a ca. 10-fold increase in absorbance at l t w49x. Protonation is not the cause of these
spectral changes since the zwitterionic form, when protonated at the phenolic oxygen, absorbs only below 450
nm. For 3 in dioxane-water the p K a value is 4.6 w23x.
The dependence of the absorption changes at 480 and 560 nm versus wH 2 Ox Fig. 4b. shows that the 50%
value is reached for ca. 2 M water. A water concentration of 0.10.3 M, typically used for dissolving the salts in
organic solvents, can therefore be tolerated in the SprM nq solutions.
k5

nq
M nqq H 2 O M aq
.

5.

ky5

The dependence of 1rwtrans-M nq x on wH 2 Ox, derived on the basis of Eqs. 1., 2., 4. and 5., is given by:

w trans-M nq x o
k4
k4
k4
2
s 1 q K5 q
q
K 2 w M nq x o w H 2 O x q
K 5 wH 2 Ox . .
nq
w trans-M x
ky2
ky1
ky2

6.

Here, the subscript o refers to the value in the absence of water. The dependence of 1rA 480 , being
proportional to 1rwtrans-M nq x, was found not to depend linearly on wH 2 Ox; instead, a further term of higher
order 2 or 3. is indicated by the experimental results. An example is shown by plotting A 0 y A m .r A y A m .
versus wH 2 Ox, where A 0 and A m refer to the values at 480 nm at - 0.1 M and maximum 0 4 M. water
concentration, respectively Fig. 4c.. This and similar dependences in other cases indicates that ky5 < k 5 , since
otherwise no square dependence versus wH 2 Ox should result.

Fig. 4. a. Absorption spectra of 3 in acetonitrile in the presence of Nd III 0.10 mM. with wH 2 Ox s - 0.1 . and 4 M - - -.; b.
absorption changes at 480 `. and 560 v . nm; and c. A 0 y A m .r Ay A m . as a function of water concentration.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

432

3.3. Fast relaxation kinetics

Complex formation by irradiation of 6-NO 2-BIPSs involves the merocyanine cis and trans isomers w49x. The
photocolouration occurs via the trans triplet state 3 trans ) . which is in equilibrium with the perpendicular triplet
configuration 3 perp ) . w1013,2831x. The proposed sequence after population of the excited singlet state is
intersystem crossing at the Sp geometry, reaction 7., ring opening in the triplet manifold 8., establishment of
equilibrium 9. between the trans and the perpendicular triplet configurations, intersystem crossing at the
perpendicular configuration and internal rotation in the ground state to the cis and trans isomers, sequence 10..
Thermal isomerization 12. yields the trans isomer Scheme 1.. The lifetime of the cis isomer of 15 in solution
at room temperature is in the micro- to millisecond range w30x. Colour formation is delayed due to the
intermediacy of the observed triplet having a lifetime of 310 ms w30x and accelerated in the presence of oxygen
due to quenching reaction 11.. The fraction of the 3 perp ) state decaying into the cis isomer under these
conditions a X . only slightly differs from that a . in the absence of oxygen a X ( a w30x..
After removal of the UV light, the enhanced colouration slowly disappears, approaching the steady-state
value at lt . The relaxation kinetics are first-order w49x and the relaxation times of 15 in acetonitrile are
t t Sp f 1rky1 s 12160 s Table 1.. The rate constant k 1 is then obtained from ky1 and K 1. For 3 in
acetonitrile, K 1 f 0.03, 1rky1 f 35 s and 1rk 1 f 1200 s and for 2 and 4 1rk 1 is smaller and in the other cases
larger. For 1, where no chelating would be expected due to the absence of a 8-methoxy group and for 5 K 1 is
significantly smaller than for 24. For 6 and 7 photocolouration in small yield. occurs via the singlet pathway
w28x.
Upon excitation of 15rM nq 0.1r0.1 mM. in the absence of oxygen, the spectra after the end of the 308
nm pulse and within a few microseconds remain the same as without additive. After 10100 ms this band at
lt s 560600 nm is converted into a new band centered at 480 nm, as shown in Fig. 5a for 3rNd III. Since the
lifetimes of the excited Sp states are too short to interact with a metal ion, not only the trans but also the cis
isomer should react with M nq, 2 forward. and 2X ., respectively.

2X .

cis q M nqtrans-M nq .

The absorption of trans-M nq at 308 nm is small with respect to that of the Sp form provided that wM nq x is low
enough - 30 mM for lantanides and ca. 0.1 mM for most other metal nitrates.. Apart from some bleaching at
l - 500 nm, we could not detect any effect of an excited complex. The spectra of the complex, the trans and cis
isomers and the TT absorption overlap; for simplicity, the triplet state was quenched by oxygen.

Scheme 1.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

433

Fig. 5. Transient absorption difference spectra in oxygen-saturated acetonitrile in the presence of 50 mM Nd III for a. 3 at 1 %., 30 I.,
100 v . and 500 ms `. after the 308 nm pulse and b. 5 at -1 %. and 100 ms ^.. Insets: signals as indicated.

For 15 and Nd III in acetonitrile the rate constant for decay at l t k obs . and formation at lcom f 480 nm are
practically identical for a fixed metal nitrate concentration insets of Fig. 5a. and depend linearly on wM nq x Fig.
6a.. Similar dependences were found for other metal nitrates. From the reciprocal slope, a fast relaxation time
t I . for the reaction of the trans andror cis isomers is obtained. For 3 in acetonitrile t I = wM nq x.y1 ranges
from - 5 = 10 7 My1 sy1 for Ni II to 1.1 = 10 9 My1 sy1 for Pb II Table 3..

Fig. 6. Plots versus metal ion concentration of a. rate constant for decay at 560r590 nm 1r3. and b. percentage of complex formation for
1 ^,`,e. and 3 ',v,l . in acetonitrile using Mg II ^,'., Pb II `,v . and Nd III e,l.; lexc s 308 nm.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

434

Table 3
Rate constant and percentage of complex formationa
M nq

1rt I =wM nq x. 10 8 My1 sy1 .

Compound:

8
19c
) 20c
- 0.2
8
17c
) 20c
25c
4
9
10
8
6

9
9
4
- 0.5 c
6
10
9
11
6
5
4
5
6

8
10
5
- 0.9
7
10
13
14
6
6
8
5
6

22
35
50
15
75
60
15
36
94
95
95
92
90

75
80
85
30
80
80
80
90
90
97
97
95
95

40
70
70
15
80
85
40
80
90
90
90
85
90

II

Mg
MnII
Co II
Ni II
CuII
ZnII
Cd II
Pb II
Y III
Pr III
Nd III
EuIII
Tb III

Ptb com %.

In oxygen- or air-saturated acetonitrile, wSpx s 0.1 mM, lexc s 308 nm.

Pt com s 1yD A t rD A 0 . for wM nq x s 0.10 mM.
c
In addition a minor slower component.

The spectra of other 6-NO 2-BIPSsrM nq systems are similar with a few exceptions. and further examples
are shown in Figs. 7 and 5b for 1 and 5, respectively. The mixture of trans and cis isomers is formed in all cases
within a few microseconds reactions 7. 10.., and the kinetics of complex formation depend on wM nq x as
described above. The observed rate constant for each given metal nitrate is similar for unidentate 1. and
bidentate 24. complexes Table 3.. BIPSs 6 and 7 in acetonitrile exhibit also photoconversion into the trans
isomer, albeit in small yield via the singlet pathway w29,30x. Consequently, uni- and bidentate complexes are
formed also with 6 and 7 lcom s 520 nm and 460 nm, respectively..
A further measure of the extent of complexation is the term Pt com s 1 y D A trD A 0 ., where D A trD A 0
refers to absorbances at lt after complex formation is completed e.g. 1 ms., relative to the initial one being
proportional to the cis plus trans mixture.. Examples are shown in the insets of Fig. 7 for 1 using four increasing
Nd III concentrations. For lantanides Pt com for a given metal ion concentration of 0.1 mM is close to 100%,
whereas it is smallest 1030%. for Ni II at 0.1 mM and intermediate for the other ions Table 3.. The suggested
reason is a difference in equilibrium constant K 2 .

Fig. 7. Transient absorption difference spectra of 1 in oxygen-saturated acetonitrile in the presence of 0.10 mM Nd III at - 2 ms '. and 0.2
ms ^. after the 308 nm pulse. Insets: signals 14 refer to wNd III x s 5, 10, 30 and 100 mM, respectively.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

435

For 1 as unidentate ligand, 2. is replaced by equilibrium 13..

k 11

k 12

ky11

ky12

trans q M nq trans . . . M nq trans-M nq .

13 .

Here, trans . . . M nq is the outer-sphere complex. The outer-sphere formation constant K 11 . is typically 0.15
My1 for interaction between a cation and a zero-charged species w52x. Pt com is then expressed by:
Pt com s

w trans-M nq x e
K 11 K 12 w M nq x o
s
.
w transx o
1 q K 11 1 q K 12 . w M nq x o

14a.

The dependence of Pt com on wM nq x o is shown in Fig. 6b. From this it follows that the limiting value for high
metal ion concentration is K 12 r1 q K 12 .. For the condition ky11 4 k 12 , the observed fast relaxation time for
reaction 13. is:
1rt I s ky12 q K 11 k 12 w M nq x o .

15a.
8

The observed forward rate constant for complex formation with 1 is typically K 11 = k 12 s 68. = 10 My1
sy1 Table 3. which gives k 12 s 46. = 10 9 sy1. This is higher than the rate constant for solvent exchange of
1.4 = 10 7 sy1 for MnII in acetonitrile w52x.
For bidentate complex equilibrium 13. is replaced by 13X ..
k 11

k 12

k 13

ky11

ky12

ky13

trans q M nq trans . . . M nq trans.-.M nq trans-M nq

13X .

Here, the latter refers to the chelate and trans.-.M nq to the unidentate complex. Pt com is given by:
Pt com s

K 11 K 12 K 13 w M nq x o
1 q K 11  1 q K 12 1 q K 13 . 4 w M nq x o

14b.

The limiting value of Pt com for high wM nq x o is K 12 K 13r1 q K 12 1 q K 13 .. For k 13 4 ky12 , i.e. the loss of the
first solvent molecule is rate determining, the relaxation time for reaction 13X . is given by:
1rt I s ky12rKy13 q K 11 k 12 w M nq x o .

15b.

For k 13 < ky12 , the relaxation time is given by:

1rt I s Ky13 q K 11 K 12 k 13 w M nq x o .

15c.

In this case, substitution of the second solvent molecule by the ligand is the rate determining step in the kinetics
of complexation. For bidentate ligands the observed forward rate constant for complex formation also lies in the
same range as for the above case with the exception of Ni II . Assuming that the rate of chelation ring closure. is
higher than the rate of the loss of the first solvent molecule, k 12 s 410. = 10 9 sy1.
3.4. Light-induced slow relaxation kinetics
UV-irradiation lirr s 313 nm. of 3 in acetonitrile in the presence of metal nitrates in small concentration
2060 mM. causes enhanced formation of the complex, as measured by the absorption increase at lcom f 480
nm. The relaxation kinetics are described by first-order equations and the slow relaxation time is the same as
that of thermal colouration, t Sp com s tcom Sp which is denoted as t II . The increases of t II with wM nq x is
shown in Figs. 2b and 3. Similar effects were observed for other 6-NO 2-BIPSs and metal nitrates Tables 1 and
2..
On the other hand, selective excitation of the complex l irr s 436 nm. or irradiation at 313 or 366 nm in the
presence of metal nitrates in larger concentration 0.10.3 mM. causes a decrease of the complex absorbance
followed by recovery slow relaxation.. Examples of increasing and decreasing absorbance due to irradiation at

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

436

Scheme 2.

313 and 436 nm, respectively, followed by relaxation are shown in the inset of Fig. 1a. To account for this
effect, initial photosubstitution of the complex and subsequent formation of the Sp form are proposed.
hn

trans-M nq 1 trans ) -M nq

16 .

17 .

trans )-M nq Sp q M nq .

An alternative suggestion could be photosubstitution of the complex, thereby forming the trans isomer. This,
however, would restore the complex within 10100 ms due to reaction 2 forward. and is therefore excluded. A
triplet state in reaction 17. is unlikely since the yield and kinetics of bleaching upon pulsed excitation see
below. and the spectral changes upon steady-state irradiation are insensitive towards oxygen. Whether or not
irradiation of the complex leads to a larger or smaller absorption at l com , depends on several factors, such as
absorption of trans-M nq and Sp or the quantum yield of reaction 17. Scheme 2..
Reestablishment of equilibria 1. and 2. occurs after i. mixing, ii. photocolouration lirr s 313 or 366 nm
in the presence of metal nitrates in smaller concentration., and iii. photosubstitution lirr s 436 or f 500 nm..
The observed relaxation time for 3 in acetonitrile increases from 35 s for wM nq x s 0 M to 700 s for
wPr III x s 0.10 mM and further to ca. 1000 s for ) 1 mM Tables 1 and 2., where the limiting value at high
wM nq x. should be 1rk 1 f 1200 s. The calculated dependence of the t II values versus log wM nq x and the results
for 3 0.10 mM. and three characteristic metal nitrates are shown in Fig. 3.
3.5. Effects of enironment
Equilibrium 1. of 6-NO 2-BIPSs is shifted to the trans side, i.e. K 1 increases, when the solvent polarity is
increased w12x, e.g. from dioxane to acetone and acetonitrile Dimroth-parameter: E NT s 0.17, 0.36 and 0.49,
respectively w53x.. For butyronitrile the E NT value should be somewhere between the latter two. A similar effect
of 1rky1 has been reported w23,24x. Because the overall charge of the trans form as ligand is zero, K 11 should
not depend on E NT . If we assume that K 2 for a given metal ion is also independent of E NT , the relative complex
concentration should be proportional to K 1. In fact, for 3 or 4 the A com rA Sp ratio shows a trend to increases
with E NT not shown.. The t II value depends essentially on ky1 and K 2 Eq. 3b.. Since ky1 in the cases
examined is rather independent of E NT Table 1. also t II for a given metal ion should behave similarly. This is
experimentally found, although other factors structure, see Mg II . also play a role.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

437

For complexation of metal nitrates in acetone we have considered that four or six water molecules could act
as ligands for M II or M III , respectively w49x. However, due to the large similarity of the results from the four
solvents used, we now propose that water as ligand in low concentration is completely replaced by the organic
bulk solution. For Nd III , Pb II and Mg II the experimental points follow the calculated dependence in the
0.020.3 mM range Fig. 3.; note that large metal concentrations cannot be achieved under the conditions of
low water content. The markedly smaller t I and t II values for Ni II with respect to other ions, such as Nd III or
Pb II Tables 2 and 3., are probably the result of a slower replacement of solvent molecules at Ni II by the
merocyanine ligand w52,54,55x. Complexation in acetonitrile, due to its better solvation ability towards metal
ions, could be different from that in acetone. However, this is not the case since most results involving
equilibria 1. and 2. are comparable or even similar.
3.6. Excited state properties of complexes
Fluorescence was detected for merocyanines in the absence w15,31x and presence of metal ions Scheme 2.
w4346,49x. The fluorescence spectrum lexc s 450530 nm. is f 90 nm blue-shifted with respect to the
non-complexed case Fig. 8.. The quantum yield is low for Co II , Ni II , Pr III or Nd III and markedly larger for
ZnII , Cd II , Pb II and Y III Table 4.. The fluorescence excitation spectrum coincides with the absorption spectrum,
which has its maximum at lcom s 480520 nm, but in some cases with small F f values the excitation
maximum is red-shifted with respect to lcom . In all cases fluorescence is a minor deactivation route at room
temperature. Preliminary results in butyronitrile at y1968C, however, show an 10100-fold increase in F f for
Y III , Pb II and ZnII , indicating that in these cases fluorescence is the major deactivation route. For complexes
with other metal nitrates, intramolecular quenching see below. or other radiationless processes are still
dominating at y1968C.

Fig. 8. Excitation left. and fluorescence right. spectra of 3 a. in acetonitrile at 258C in the presence of Pr III - -. and Pb II . and
b. with Y III in butyronitrile at 258C . and y1968C - - -.; lexc s 500 nm, lf s 630 nm.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

438

Table 4
Fluorescence maximum of the complex and quantum yielda
Compound:

M nq

lf nm.

F f =100

lf nm.

F f =100

625
620
-600
-600
630
640
640
620
600
620

0.5
0.2
- 0.1
- 0.05
0.8
0.3
0.6
1.0 1.5. b
0.1
0.05

610

0.5

620
630
635
600
600
600
605
600

0.6
0.4
0.4
1.2
0.05
0.08
0.3
0.1

II

Mg
MnII
Co II
Ni II
ZnII
Cd II
Pb II
Y III
Pr III
Nd III
EuIII
Tb III
a
b

625

0.2

In air-saturated acetonitrile, A 500 s 0.3, lexc s 500 nm.

In acetone, Ref. w49x.

The transient absorption spectrum of 3rPb II 0.1r0.1 mM. in acetonitrile lexc s 530 nm. shows two
absorption peaks at 440 and 600 nm and two bleaching areas, one below 400 nm and one with maximum l bl .
around 480 nm Fig. 9., which coincides with the ground state maximum. Essentially, the first-order decay is
the same in the whole spectrum. The photoreaction is attributed to trans cis photoisomerization of the
complex followed by the cis trans back reaction w49x the cis isomer is shown in one of its possible
structures..

Under the conditions of selective excitation of the complex, reactions 19. 22. should be operative Scheme
2..
3

perp )-M nq perp-M nq a cis-M nqq 1 y a . trans-M nq

21 .

perp )-M nqq O 2 a X cis-M nqq 1 y a X . trans-M nqq O 2 .

22 .

The spectra and kinetics of the complexes are, to a certain extent, different in the presence and absence of
oxygen. For 3rPb II under argon the absorption peak at 440 nm contains a fast decay and a permanent
component. The fast decay at 440 nm is quenched by oxygen and the absorbance of the peak at lcis s 580 nm is
enhanced. The bleaching maximum is at 500 nm, both under argon and oxygen and the kinetics are slightly
changed by oxygen due to formation of different species, as detected also by absorption. An assignment of the
transient at lcis to a triplet state, e.g. 3 trans )-M nq is unjustified because of the rather small effect of oxygen on
the decay kinetics. The delayed formation of cis-M nq for 3rPb II in argon-saturated acetonitrile Fig. 9. is due

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

439

Fig. 9. Transient absorption difference spectra of 3rPb II 0.1r0.05 mM. in argon-saturated acetonitrile at 0.1 ms `., 10 ms '. and 100
ms I. after the 530 nm pulse. Insets: signals as indicated.

to equilibrium 20. and sequence 21.. The spectral changes are essentially similar for all combinations of
merocyanine and metal ions, but the yields are much lower than for 3 Table 5. or 4 with Pb II .
For a low Pb II concentration of 30 mM the decay in the 460700 nm range, apart from a small residual
bleaching, follows first-order kinetics with a lifetime of ca. 30 ms. The rate constant for decay and to a certain
extent also for the bleaching recovery. depends almost linearly on the Pb II concentration. Similar quenching
effects, mainly linear dependences on the metal ion concentration, were observed in all cases, where the yield
was large enough to be detected. The values for the slope k 23 . of these dependences for 3 and 4 in acetone or
acetonitrile are in the range 620. = 10 8 My1 sy1, assuming that the quenching is only due to the metal ion.
The bleaching signal D A r . measured at 0.1 ms after the pulse Table 5. remains constant ) 0.1 s. in most
cases, but for MnII or ZnII a further decrease in the millisecond range was observed around 440 nm. An
example is shown for 3rZnII Fig. 10.. The reversible spectral changes in the presence or absence of oxygen are

Table 5
Relative yields of triplet, initial transient bleaching, photosubstitution and trans cis photoisomerization for the complex with 3 a
M nq

D AbTT

y D Ac0

y D Adr

D Aet c

Mg II
MnII
Co II
Ni II
ZnII
Cd II
Pb II
Y III
Pr III
Nd III
EuIII
Tb III

0.2
0.5
- 0.04
- 0.04
0.5
0.5
1.0
0.1
0.2
0.1
0.5
0.5

0.4
0.9
- 0.03
- 0.03
0.9
0.3
0.9
0.6
0.1
0.05
0.6
0.6

0.2
0.5
- 0.02
- 0.02
0.5
0.1
0.3
0.4
0.1
0.05
0.4
0.4

0.2
0.4
- 0.05
- 0.05
0.6
0.3
1.0
0.3
0.2
0.2
0.4
0.4

In acetonitrile normalized for each column., A 530 s 0.3, lexc s 530 nm.
Difference at 430 nm between 0.02 and 2 ms under air. due to TT absorption.
c
Total bleaching at f 480 nm after 2 ms.
d
Remaining bleaching at f 480 nm after 0.1 ms.
e
Absorption at 590 nm due to transcis photoisomerization.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

440

Fig. 10. Transient absorption difference spectra of 3rZnII 0.1r0.10 mM. in oxygen-saturated acetonitrile at -1 ms `., 0.1 ms \. and 1
ms B. after the 530 nm pulse. Insets: signals as indicated.

due to trans cis photoisomerization. Consequently, the observed quenching effect is due to thermal cis trans
isomerization which is accelerated by the metal ion or water w49x.
cis-M nqq M nqrH 2 O trans-M nqq M nqrH 2 O .

23 .

II

When water was added to the 3rPb 0.1r0.1 mM. acetonitrile system, a linear dependence of k obs at 580 nm
versus wH 2 Ox and a rate constant of k 23X s 5 = 10 5 My1 sy1 were obtained not shown.. Therefore, reaction
23X . is proposed as second pathway for cis trans isomerization,
nq
cis-M nqq H 2 O trans aq q M aq

23X .

followed by forward reaction 2., which is generally fast enough to hinder observation of trans aq as intermediate
prior to trans-M nq. The reason for the weak irreversible bleaching at - 450 nm at longer times in the presence
of ZnII inset of Fig. 10. w45,49x, MnII or Y III may be related to a second photosubstitution involving another
isomer than the observed trans form.
To account for the small photochemical yields in the presence of Co II or Ni II reaction 24. is proposed
Scheme 2.. The energy of this excited complex is dissipated by intramolecular quenching, probably via energy
transfer. Data in Table 5 show that D A at the pulse end and l cis s 580 nm, as a measure of the yield of
trans cis photoisomerization, is most efficient for Pb II , negligible for Ni II or Co II and with medium efficiency
for most other metal nitrates.
The transient absorption at lcom after disappearance of the cis isomer yD A r ., as a measure of the yield of
photosubstitution of the complex, reaction 17., is relatively efficient for Pb II , ZnII and MnII , small for Pr III or
Nd III and negligible for Ni II or Co II . This effect is in agreement with absorption changes upon steady-state
irradiation see above..
3.7. Effects of metal ion
A crown ether derivative containing 1 as two ligands and LaIII was recently reported to be significantly
stabilized by the two phenolic oxygen molecules w56x. In our systems with 1:1 stoichiometry, there is also a
larger stability of the bidentate complexes with lantanides, as expressed by the experimental A trA Sp ratio
Table 2., being roughly proportional to K 2 for a fixed Sprsolvent combination. For nearly all cases examined,
K 2 increases in the order Ni II , Mg II , MnII , Cd II , Co II , Pb II , ZnII and Y III and even higher values for the other
lantanides. Since K 11 may be regarded as independent of the type of metal ion, the specificity of the metal ion
should be mainly due to K 13 , i.e. the effect of chelation by the five-membered ring. In this respect 3 or 4 in
acetonitrile with Nd III or Pr III are the most stable complexes.

A.K. Chibiso, H. Gornerr

Chemical Physics 237 (1998) 425442

441

Concerning the photoprocesses, the most interesting complexes are 3 or 4 in acetonitrile with Pb II since the
yield of fluorescence is moderate Table 4. and those of intersystem crossing and trans cis photoisomerization
are highest Table 5.. These systems show also photosubstitution, albeit it plays a dominant role only for MnII
and ZnII . By variation of relevant parameters, such as medium, structure, metal ion and concentrations, the
relaxation kinetics as well as the photochemistry are fully controlled. The studies in this work were carried out
with relatively low Sp and metal ion concentrations. However, when the Sp concentration is strongly increased,
it should be possible to produce almost uniform absorbance in the VIS spectral range which can find new
application.

4. Conclusion
Complexation of spiropyrans with metal ions in solution is the result of two coupled reactions: formation of
merocyanine-type ligand and substitution of the solvent coordinated at the metal ion. by the ligand. This is
characterized by two relaxation times reflecting fast and slow kinetics, t I and t II , respectively. The overall rate
of thermal complexation is limited by the rate of thermally activated ring opening, whereas the rate of
light-induced complexation is determined by the rate of thermal substitution. For the trans isomer of
6-NO 2-8-OMe-BIPSs as bidentate ligand the rate of complexation is limited by that of replacement of a solvent
molecule. The slow relaxation time is independent of the method of perturbation by: i. mixing of ligand
solution with metal ions, ii. UV irradiation of Sp in the presence of metal ions and iii. irradiation of
complexes. t II increases with concentration of metal ion and reaches an upper limit which is determined by the
time needed for ring opening. For several uni- or bidentate ligands the fast relaxation time t I is similar and
shorter than 0.1 ms. for most metal ions - 0.1 mM., except for Ni II , indicating that loss of the first solvent
molecule is rate determining. The decrease of the equilibrating complex concentration on addition of water is
due to both ligand replacement in metal-complexed ion and non-complexed metal ions by water. The pulsed
photochemical perturbation of equilibria 1. and 2. studied in this work has some striking advantages in
comparison with other relaxation methods, such as T-jump, and can be applied to systems with strongly shifted
equilibria and for non-aqueous solutions.

Acknowledgements
We thank Professor K. Schaffner for his support and Mr. L.J. Currell for technical assistance. AKC thanks
the Deutsche Forschungs-gemeinschaft and the Russian Fund of Basic Researches No. 97-03-32136. for
financial support.

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