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PAPER www.rsc.org/materials | Journal of Materials Chemistry

Micro-environmental fine-tuning of electronic and kinetic properties of

photochromic dyes
Jamie Whelan,a Dalia Abdallah,b James Wojtyka and Erwin Buncel*c
Received 2nd March 2010, Accepted 14th April 2010
First published as an Advance Article on the web 8th June 2010
DOI: 10.1039/c0jm00585a
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Despite the recognition of the importance of Spiropyran (SP)–Merocyanine (MC) photochromic

materials in molecular switching, the majority of studies have been reported in solution with relatively
few in the solid-state as required in modern displays and other devices. In contrast, the present work
bridges solution, condensed phase and solid-phase media and is to our knowledge the first micro-
environmental study on electronic and kinetic effects for the SP–MC system. Expanding on our
previous work we have investigated the photochromic properties of an SP molecule (1b) attached to
a 100 mm commercially available polystyrene micro-particle (Wang Resin). The thermal MC / SP
reversion kinetics (5a,b / 4a,b and 2a,b / 1a,b) which reflect the critical lifetime of the open MC form
were measured. Reduction in kobs of thermal reversion, MC / SP, up to two orders of magnitude, and
a blue-shift up to 58 nm was observed with the potential for tailoring or fine tuning. The use of
polymeric micro-particles in controlling both electronic and kinetic properties of photochromic
molecular switches has been highlighted.

Introduction a first-order reaction. This SP-MC interconversion is accom-

panied by a change in colour (from colourless SP to coloured
The fields of micro-1 and nanoelectronics2 have received much MC), a change in polarity (non-polar SP to polar MC) as well
activity in the past decade, the recent focus being on materials as the aforementioned change in shape (orthogonal SP to
whose properties can be easily manipulated by application of planar MC).
heat, electron injection, or light. Many of these studies have Various efforts have been made to exploit the photochromic
utilised compounds known as molecular switches, the basic nature of spiropyrans towards development of information
premise being that application of an external stimulus causes storage systems,12 MRI contrast agents,13 metal ion sensors,14
a reversible structural/chemical change to occur. Examples of fluorescent probes15 and photoswitchable magnets.16 An impor-
molecular switches under investigation include azobenzenes,3 tant factor in implementation of these and other SP-based
diarylethenes,4 fulgides,5 spirooxazines,6 spiropyrans7 and a new applications is the thermal reversion reaction, MC / SP. Many
family based on [1,3]oxazine rings.8 attempts have been made to suppress reversion, including
Spiropyrans are a class of compounds symbolic of molecular chemical modification,17 phenoxide protonation,18 metal ion
switches due to their thermochromic (heat),9 electrochromic chelation,19 as well as choice of solvent.20 Degradation of the
(electron injection)10 and photochromic (light exposure)11 SP–MC photochromic switch, or ‘‘fatigue’’ effects, upon repeti-
properties. The spiropyran (SP) molecule is composed of two tive switching cycles remains an issue for their long term use, with
moieties, linked via a sp3 spiro-carbon (Scheme 1), imposing both O2-dependent and O2-independent processes observed.21
orthogonality on the molecule. Excitation of SP upon irradia- Formation of the triplet-excited state following UV irradiation
tion in the UV (ca. 350 nm) results in heterolytic cleavage of of the SP and prior to ring opening is known to result in the
the spiro-carbon–oxygen bond, with subsequent cis-trans iso- formation of singlet oxygen,22 and an improvement in cycling
merisation producing an extended p-orbital isomeric system, efficiency has been observed on addition of singlet oxygen
the merocyanine (MC). Accordingly, this new planar MC scavengers.23
absorbs in the visible spectral region (ca. 550 nm) and in polar SPs have been well studied in solution,24 and of late research
solvents displays a degree of charge separation which is sche- has begun to focus on the physical and chemical properties of SPs
matically represented as a zwitterionic resonance structure; in the solid-state. Work undertaken includes metal electrodes
non-polar solvents inhibit this charge separation, resulting in usage,25 nanoparticles,26 polymer nanoparticles,27 as well as
greater quinoidal character (Scheme 1). Thermal energy or several publications on attachment to polymer brushes.28 Work
visible light irradiation reverses the ring-opening process in carried out by Li and co-workers has examined the photo-
chromic properties of SP molecules attached to the periphery of
a
Department of Chemistry and Chemical Engineering, Royal Military nanocrystals with the aim of modulating crystal fluorescence.29 It
College of Canada, Kingston, ON, Canada K7K 7B4 was found that the open MC isomeric form of the dye quenched
b
Reserves Development Division, Abu Dhabi Company for Onshore Oil
Operations, P.O. Box 270, Abu Dhabi, United Arab Emirates
the nanocrystal fluorescence via a FRET mechanism, while the
c
Department of Chemistry, Queen’s University, Kingston, ON, Canada SP isomer had no such effect. Following this, the authors
K7L 3N6. E-mail: [email protected] incorporated SP molecules in hydrophobic cavities of polymer

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Scheme 1
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nanoparticles and observed a fluorescence behaviour of the Gaining insight into the fundamentals of solid-state kinetic
encapsulated MC.30 behaviour is central towards integration of the SP-MC molecular
Recently we have shown how a simple photochromic micro- switch into novel micro- or nanotechnologies.
particle could be synthesised from readily available starting
materials using the cross-linked polystyrene Wang Resin (WR) Results
as solid support and following the kinetics of thermal MC / SP
reversion in condensed medium.31 For better understanding of 1. Synthesis and characterisation of photochromic
the potential uses of the SP system in microelectronic devices, microparticles
blade-coated thin film samples of the molecular dye and the two From a family of insoluble polymer beads,32 the cross-linked
photochromic microparticles were prepared and the kinetics of polystyrene Wang Resin (WR)33 (3) containing tethered
thermal reversion followed. Thus herein we build on our hydroxymethyl reactive sites was chosen as the solid support
previous work by varying the photochromic microparticle size, (Scheme 2). Coupling with the carboxylated SP34 (1b) formed the
whilst also developing solid film studies. Synthesis and charac- photochromic microparticle WR-SP (4), which upon UV irra-
terisation of the photochromic microparticle will be detailed first, diation converts into WR-MC (5). Structural characterisation
followed by spectral and kinetic studies of the micro-particles in was carried out using FT-IR spectroscopy showing proof of
condensed phase (non-polar viscous medium). Thereafter, these attachment, and 1H-MAS to determine percentage of resin
measurements will be repeated on particles in the solid state by reactive sites containing SP molecules following a previously
incorporation into thin films, and comparison made of all reported procedure.35
systems with free SP in solution. Two particle sizes were chosen, 50 and 100 mm, designated as
The use of photochromic particles in fine-tuning the electronic 4a (WR-SP 50 mm) and 4b (WR-SP 100 mm), producing coloured
properties of molecular switches is discussed employing the SP- particles labelled 5a (WR-MC 50 mm) and 5b (WR-MC 100 mm)
MC as a model system, including consideration of particle size. following UV irradiation. Previously 1b was chosen having
Our work shows the potential for incorporation of the SP-MC a suitable linker group for attachment to the resin. Additionally,
photochromic molecular switch into solid-state technologies. 6-nitro-BIPS (1a) is used herein for comparative purposes.

Scheme 2

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2. Kinetics of thermal reversion in condensed medium

Though 3 is known to swell in various solvents,36 the polymer

particles eventually sediment to the bottom of a vessel. To
combat this, the solution can be ‘‘hardened’’ with a suitable
thickener. Since the SP-MC system is sensitive to changes in
solvent polarity, an appropriate system was required so as not
to distort the kinetic experiments. Given that 3 is composed of
cross-linked polystyrene, the solvent and thickener chosen
which most matched this was toluene and polystyrene.
Reichardt’s dye37 was used to monitor the polarity changes
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between toluene and the polystyrene thickened toluene. No

change in polarity was observed up to a medium viscosity of
11 centi-Stokes (cS), the condensed medium employed in this
study. Fig. 2 Solid state first order rate plot of thermal reversion 5a / 4a in ca.
Kinetics of thermal reversion, MC / SP, were followed 750 mm polystyrene matrix thin film (kobs ¼ 7.25  104 s1).
spectrophotometrically in a quartz cuvette with both 4a and,
separately, 4b, suspended in condensed medium. The thermal
reversion process WR-MC / WR-SP follows first order
kinetics, with results for both photochromic microparticles 4a Table 2 Observed rate constants and lmax for the kinetics of thermal
and 4b, as well as for unbound photochromes (1a and 1b) in reversion MC / SP, for 2a, 2b, 5a and 5b in the solid state
condensed medium and in solution given in Table 1. Kinetic process kobs, s1 (MC lmax)

2a / 1a 9.72  104 (596 nm)

3. Solid state kinetics 2b / 1b 10.5  104 (596 nm)
5a / 4a 7.25  104(588 nm)
Homogeneous films of the photochromic systems under study 5b / 4b 5.69  104(588 nm)
were prepared from a blade-coated toluene/polystyrene solution
(1)/suspension (4a and 4b), yielding a film thickness ca. 120 mm
and ca. 750 mm, respectively. After irradiation UV-Vis spectra
were recorded and kinetics of MC / SP thermal reversion
followed (Fig. 1 and 2). All thermal reversion reactions fol-
Table 1 Observed rate constants and MC lmax for thermal reversion 2a lowed first-order kinetics and solid-state results are given in
/ 1a and 2b / 1b in solution and condensed medium, and 5a / 4a and Table 2.
5b / 4b in condensed medium

kobs, s1 (MC lmax)

Discussion
Kinetic process Solution Condensed medium
1. Medium polarity effects
2a / 1a 12.2  102 (600 nm) 13.1  102 (600 nm)
2b / 1b 6.94  102 (604 nm) 7.43  102 (604 nm) Medium polarity is of paramount consequence for the SP–MC
5a / 4a 32.2  104 (588 nm) photochromic system. Previously our group and others
5b / 4b 38.7  104 (588 nm) have observed colouring and kinetic effects induced by solvent
(solvatochromic and solvatokinetic behaviour) on a number of
SP-MC systems.20,37 It was found that an increase in solvent
polarity, as measured by Reichardt’s dye, resulted in a hyp-
sochromic shift in lmax of the coloured MC form, as well as
a decrease in kobs for thermal MC / SP reversion. Scheme 1
shows the typical schematic representation of the SP-MC
interconversion, namely that structurally and electronically the
coloured MC isomeric form is situated somewhere between two
resonance forms, quinoidal (non-polar media) and zwitterionic
(polar media). Depending on the predominant resonance
structure, a thermally-induced back reaction would reduce to
C–C single bond rotation (5 kcal mol1) for quinoidal MC
with electrocyclic ring closing, vs. trans / cis C]C isomer-
isation (65 kcal mol1) for zwitterionic MC, followed by C–O
bond recombination. Viewing the above as an increase in
solvent polarity resulting in an increase in bond order of the
central C–C bond, non-polar solvents favour greater quinoidal
Fig. 1 Solid state first order rate plot of 2a / 1a thermal reversion in ca. character, while polar solvents favour a more charge-separated,
120 mm polystyrene-matrix thin film (kobs ¼ 9.72  104 s1). or zwitterionic (hybrid) resonance form as illustrated.

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compared the band maximum of their MC in water (525 nm) to

that of their MC-nanoparticles in water (588 nm) and concluded
that the MC is situated in a hydrophobic environment. In the
present case, however, the solvent polarity is not being altered, the
condensed medium of toluene/polystyrene having the same
polarity as cross-linked polystyrene resin. Thus another factor
must be causing this decrease in lmax, which is likely to be a change
in the micro-environment of the open form, on going from a free-
Solvatokinetic studies showed that kobs for the thermal moving fluid solution, to a more confined polymer micro-partic-
reversion was only moderately influenced by solvents of low ulate environment. Interestingly, in our case and that of the
polarity, e.g., toluene, diethyl ether and 1,4-dioxane. The mech-
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MC-polymeric nanoparticle of Li and co-workers, the MC isomer

anism in non-polar solvents for ring-closure of MC to SP is thus becomes encased within a hydrophobic environment; the authors
considered as an electrocyclic process via the transition state as conclude that the red shift of their MC attached to the periphery of
shown.20 a nanocrystal is due to the non-polar micro-environment on the
In the present study we set out to determine the effect of particle surface. Lowering of lmax indicates a restricted orienta-
changes in the micro-environment on the electronic and kinetic tion of the MC enforced by the resin, thereby limiting the degree to
properties of the SP-MC system, building on the results of our which MC can achieve its lowest energy state, i.e. planar form. The
group’s previous works. Changing the solvent medium within the issue of planarity is important here as it is the extended p-conju-
non-polar range results in little change in both lmax and kobs,20 gated network formed upon ring opening which gives rise to the
unlike in polar solvents. This is deemed to be a key requirement coloured MC form, not present in orthogonal SP. A reduction in
from which to judge the micro-environmental effects on the planarity hampers MC attaining its lowest energy state
energies and kinetics of thermal reversion. It is expected that the (i.e. reduced planar structure), evidenced by a decrease in lmax.
quinoidal resonance character will predominate in toluene, Kinetic results (Table 1) in condensed medium show that kobs
chosen as base solvent. for MC / SP thermal reversion decreases by two orders of
Two parameters are expected to exert influence on the UV-Vis magnitude, comparing 2a (13.1  102 s1) and 2b (7.43 
absorption and kinetic properties of this molecular switch 102 s1) to 5a (32.2  104 s1) and 5b (38.7  104 s1); results
comprising solution, condensed and solid-state systems: for 5b mirror those for 5a. The decrease in rate of reversion can
(i) polarity, and (ii) state of micro-environment, i.e. solution, be rationalised as resulting from constraints imposed by the
condensed, solid. In this study, polarity as measured by Reich- polymer resin. For thermal back reaction, a volume demanding
ardt’s dye is held constant; however, interaction between MC process, in condensed medium of the resin-bound MC vs. free
and the micro-environment marks important change as one MC, the obstacles put in place by the polymer strands of the resin
traverses over solution, 2a and 2b (toluene); to condensed 2a and could hinder the MC’s ability to rotate about the central C–C
2b (toluene-polystyrene); condensed particulate, 5a and 5b bond, i.e. the polymer microparticles’ entangled internal strands
(toluene-polystyrene); to solid-state 2a and 2b (polystyrene obstruct efficient rotation of the dye molecule, thus prolonging
matrix); and finally solid-state particulate, 5a and 5b (polystyrene the life-time of the MC isomer.
matrix). Concurrently, UV-Vis examination of photochromes 2a Condensed phase photostability studies carried out on 5b
and 2b in toluene shows lmax 600 and 604 nm, and thermal closely resemble 5a, with the cycling ability of the photochrome
reversion rates for MC / SP, kobs ¼ 12.2  102 s1 (2a) and 5b and 5a relative to 2a and 2b increased by over 200% and 300%
6.94  102 s1 (2b), respectively. Using this as our baseline, all respectively. Li and co-workers found that binding of the dye to
other systems will be compared on the basis of changing a nanocrystal had no effect on photodegradative reactions;28
parameter (ii) above. however, the authors noted that incorporation of the dye into
a polymer particle minimized bimolecular degradative reactions
proceeding via the triplet-excited dye molecules.29 The corre-
2. Condensed Phase Study of MC / SP Reversion
spondence of our results with their system suggests similar
Variation in medium viscosity, from 1 to 11 cS, for 2a and 2b in reasoning here.
non-polar range was found to result in no change in lmax and Progression in the micro-environment from solution to
minimal change in kobs relative to baseline toluene. This implies condensed medium, followed by incorporation into a polymer
that rotation about the central C–C single bond is unimpeded in microparticle, warranted further insight regarding future appli-
viscous media for the free, unbound, MC. cations of this system; thus a solid-state investigation was initi-
Concomitant to attachment of carboxylated SP (1b) to WR (3) ated. As with condensed medium analysis, solid-state kinetics of
forming 4a and 4b, lmax of the open form in condensed medium thermal reversion of MCs 2a, 2b, 5a and 5b will be compared to
was found to shift from 600 (2a)/604 (2b) nm to 588 nm (both 5a that of solution (2a and 2b) and condensed systems (2a, 2b, 5a
and 5b). Based on solvatochromic studies outlined earlier, this and 5b).
shift would normally coincide with an increase in solvent polarity,
in accordance with increasing stabilisation of the developing
3. Solid-state Studies of MC / SP Reversion
zwitterionic resonance form. The results bear a striking similarity
to the 588 nm absorption lmax found by Li and co-workers in both (a) Micro-environmental spectroscopic observations. The UV-
their MC-nanocrystal24 (THF) and polymeric MC-nanoparticle Vis spectra of the prepared films of 1a and 2a (Fig. 3), and 1b and
beads29 (polystyrene-based in water). Li and co-workers have 2b (Fig. 4) following irradiation are pertinent. Fig. 3 shows lmax

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Fig. 3 Solid state UV/Vis spectra of 1a (SP) and 2a (MC) in ca. 120 mm
polystyrene matrix thin film.

Fig. 5 Solid state UV-Vis spectra of 4a (WR-SP 50) and 5a (WR-MC 50)
in ca. 750 mm polystyrene-matrix thin film.

As with the spectral characterisation of 2a in the solid state,

exhibiting a shoulder at 575 nm (Fig. 4), a similar and yet more
pronounced shoulder at 575 nm is seen for 5a and 5b (Fig. 5). It is
noted this shoulder peak appears at the same wavelength
(574 nm) in two different systems, solid state 2a and solid state 5a
and 5b. The UV-Vis spectrum of 2b would suggest a medium
polarity close to that of ethanol.20 It is also worth noting that
there are two distinct peaks, 546 and 446 nm (the peak at 446 nm
was seen to decay within the same time period as that of 546 nm).
The micro-environmental effect on lmax of the MC could
potentially serve as a fine tuning feature of electronic properties
of photochromic molecules. As can be seen with the free MC 2a
Fig. 4 Solid state UV/Vis spectra of 1b (SP) and 2b (MC) in ca. 120 mm in solid state compared to condensed medium, a small blue-shift
polystyrene matrix thin film.
in lmax is observed (600 to 596 nm), while attachment to the
polystyrene resin produces a further blue-shift (600 to 588 nm).
of 2a as 596 nm, shoulder at 575 nm, which represents a slight Of note is the observation that there is no variation in MC lmax
hypsochromic shift (4 nm) in lmax on progression from solution for 5a or 5b, implying a lack of MC sensitivity towards macro-
(600 nm) to solid state (596 nm). With no change in medium environmental, compared to micro-environmental, effects. From
polarity, this strongly points to micro-environment effected an optoelectronic device perspective this means freedom of
restriction of MC planarity inducing higher energy excitation for choice in terms of particle size, though the lower limits of this
backbone p-electrons. It is noted that the reduction in planarity effect still need to be established.
of condensed 2a going to solid state 2a is less than for condensed It would be of interest to study varying the degree of cross-
1a to condensed 5a (4 vs. 12 nm). Ring-opening in the solid state linking in 3 and its effect on spectral properties. If resin cross-
for 2a causes permanent deformation in the solid polystyrene linking restricts achievement of planarity, then this could be used
matrix, allowing for formation of planar MC. In comparison, for for further fine tuning of electronic properties. As noted by Li
5a the polymeric strands of Wang resin are cross-linked, thereby and co-workers,29 it is also possible that adjusting the length of
restricting the degree to which SP can fully ring open, thus the tethering chain from the SP to the resin (currently 3 carbons)
forming MC with a reduced planar structure and therefore could enable the indoline moiety more/less manoeuvring capa-
a lower MC lmax. bility, thereby minimising/maximising the lmax shift. Clearly,
The UV-Vis solid-state spectra of 4a and 5a (Fig. 5) are further defining studies would help elucidate the relationship
identical to 4b and 5b with lmax (5a, 5b) 588 nm, as found for the between the tethering chain length and the degree of crowding on
condensed phase lmax of both particles. Given the change in the electronic properties of the dye.
micro-environment from condensed to solid state, it is not
unreasonable to expect a blue-shift in lmax on going from solu- (b) Micro-environmental kinetic observations. Solid state MC
tion to solid state as observed for 2a and 2b. The polystyrene / SP thermal reversion followed at 596 nm (2a) and 548 nm (2b)
strands from the film matrix do not affect the degree to which exhibits first order kinetics with kobs ¼ 9.72  104 (Fig. 4) and
MC can achieve planarity, in contrast to the resin itself. Thus 10.5  104 s1 for 2a and 2b, respectively, and represents
planarity is determined by 3 alone, and is unaffected by the a marked decrease in kobs MC / SP from solution/condensed
greater environment. to solid state for 2a (12.2  102 to 9.72  104 s1) and 2b

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(6.94  102 to 10.5  104 s1). It also represents an increase in All glassware used in this study was cleaned in the following
the lifetime of the coloured MC isomer from that of the resin- way: washed with acetone and then soaked in an acid bath (2 M
bound micro-particle suspended in condensed medium, 32.2  HCl) overnight. The glassware was then washed thoroughly with
104 s1 (5a in condensed medium) to 10.5  104 s1 (2b in solid deionised water, then acetone, before being dried overnight in
state). Once again the progression towards a more confined/ a vacuum oven at 60  C.
restrictive micro-environment yields a further decrease in MC /
SP thermal reversion. Thus, the MC micro-environment prog-
Synthesis of 4
resses from one in which MC is free to undergo reversion
(solution/condensed medium), to one in which it is slightly In a 100 ml conical flask, 3 (1.006 g, 50 or 100 mm, 1.0 mmol g1)
crowded (condensed medium immobilised within a swollen was allowed to become swollen in dried tetrahydrofuran (THF)
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polystyrene resin), to a more crowded system (solid state) with (25 ml) for 30 min. To this suspension was added the SP (0.380 g,
the film matrix polystyrene strands expected to act as obstruc- 1 mmol), dicyclohexylcarbodiimide (DCC) (0.226 g, 1.1 mmol)
tions for ring closing, thereby decreasing kobs. It could be and dimethylaminopyridine (DMAP) (0.035 g, 0.29 mmol). The
reasonably expected, therefore, that solid state kinetics of 5a and mixture was mechanically shaken at room temperature for 6 h,
5b would reveal further decreases in kobs for thermal reversion, under nitrogen. The resin was then vacuum-filtered and washed
due to additional crowding imposed by the resin, coupled with consecutively with THF, acetone, EtOH, water and finally
the film matrix, as is indeed observed. Once again it should be acetone. The resin beads were then dried in a vacuum oven
noted that the effect of particle size is insignificant, in this case in overnight, at 50  C, to give 4a (1.130 g). Synthesis of 4b
terms of affecting thermal reversion kinetics. Coupled with the followed the same procedure (Scheme 3).
lack of influence of particle size on MC electronic properties, this
is a strong positive towards using microparticle-encased photo-
Solvent Polarity, ET(30)
chromic molecular switches for optoelectronic devices.
Table 3 records a summary of the kinetic behaviour from Solvent polarity measurements were carried out on all viscosity
solution, to condensed, to solid state media of 2a, 2b, 5a and 5b. ranges for the non-polar medium using Reichardt’s dye as indi-
It can clearly be seen that at constant polarity, modification of cator [ET (30)]. Briefly, a stock solution of Reichardt’s dye in
the micro-environment surrounding the coloured MC form plays DMSO was prepared (102 M). A sample of viscous solvent
a dominant role in determination of both electronic as well as (2.0 ml) was added to a quartz cuvette and a blank spectrum was
kinetic properties of this photochromic system. acquired. Next, 10 mL of dye solution was added to the cuvette
via syringe and placed in the UV-Vis spectrophotometer. A
UV-Vis spectrum was recorded and from lmax the ET (30) was
calculated.
Experimental
UV-Vis spectra and kinetics were recorded using a Varian Cary 3 Non-polar viscous medium
double-beam spectrophotometer equipped with a thermostatted
cell compartment set to 25  C. 1H-MAS spectra were recorded on A stock solution of non-polar medium was prepared by weighing
a Bruker Avance-600 MHz spectrometer, using a Magic Angle 42 g of polystyrene (Mw ¼ 70, 000) into a conical flask and dis-
Spinning probe. Viscosity measurements were carried out on solved in toluene (150 ml). Solutions of varying viscosity were
a Lauda viscometer, at 25  C, using an appropriate capillary prepared by changing the amount of stock solution added. For
tube. Results are quoted in centi-Stokes (cS). Solvent polarity example, 5 ml of stock solution was added to a 25 ml volumetric
was determined using Reichardt’s dye. TGA and DSC flask and this was made up to the mark with spectophotometric
measurements were carried out using a TA Instruments TGA
2050 (400  C @ 10  C min1) and a TA Instruments DSC 2010
(200  C @ 10  C min1), respectively.

Table 3 Observed rate constants and lmax for the kinetics of thermal
reversion 2a/ 1a, 2b / 1b, 5a / 4a and 5b / 4b in solution,
condensed medium and the solid state

kobs, s1, (MC lmax)

Kinetic Condensed Solid

process Solution medium state

2a / 1a 12.2  102, 13.1  102, 9.72  104,

(600 nm) (600 nm) (596 nm)
2b / 1b 6.94  102, 7.43  102, 10.5  104,
(604 nm) (604 nm) (546 nm)
5a / 4a 32.2  104, 7.25  104,
(588 nm) (588 nm)
5b / 4b 38.7  104, 5.69  104,
(588 nm) (588 nm)
Scheme 3 Synthesis of 4

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grade toluene to give a viscosity of 1.08 cS. Subsequent samples Kinetic analysis of thin film samples
were prepared in identical manner.
A sample of the SP or WR-SP thin film was cut (ca. 1  5 cm)
and this was placed across the multi-cell chamber of the HP
UV-Vis spectrophotometer. A spectrum was recorded as
Kinetics of Condensed Phase WR-MC / WR-SP ‘‘Blank’’ and then the photochromic film was placed in the
Thermal ring-closing WR-MC / WR-SP was followed by the Spectroline CX Series Ultravioloet Fluorescence Analysis
creation of a stable suspension of the photochromic beads in Cabinet equipped with a Spectroline XX-15N UV lamp (dual
a suitable viscous solution. The suspension was formed by add- 15W, 365 nm) and irradiated for 90s, generating the coloured
ing WR-SP (20 mg) to a quartz UV-Vis cuvette which was MC isomer as evidenced by the change in colour of the photo-
manually shaken to distribute the beads within the viscous chromic film. The coloured thin film was then placed back in
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media. Stability of the suspension was verified by monitoring the the spectrophotometer and the kinetics of thermal reversion
lmax of the WR-SP in the non-polar viscous media to ensure no MC / SP followed at the respective MC lmax for 10 h. Spectra
sedimentation occurred during the time frame under study were recorded every 30 s. Throughout this entire procedure,
(30 min). Once a solvent viscosity was found that generated lights were kept off and the UV-Vis spectrometer was covered
a stable suspension, a fresh sample was prepared with 2.0 ml of with aluminium foil to prevent any stray light causing unwanted
viscous solvent and 10 mg of uncoloured WR-SP particles photochemical reversion of the MC / SP. Observed rate
added to a quartz cuvette, placed in the spectrometer and constants, kobs, for thermal reversion MC / SP were calculated
a ‘‘Blank’’ spectrum recorded. The sample cuvette was then fromlinear plots of log(AN – At) versus time.
placed in a Spectroline CX Series Ultravioloet Fluorescence
Analysis Cabinet equipped with a Spectroline XX-15N UV lamp
(dual 15W, 365 nm) and irradiated for 90 s, generating the col- Conclusions
oured WR-MC isomer as evidenced by the blue colour change of In keeping with the growing need for solid-state studies of
the micro-particle. The cuvette was immediately placed into the photochromic dyes as required in modern displays and other
spectrophotometer and the kinetics of thermal reversion WR- devices, the present work has bridged solution, condensed phase
MC / WR-SP was followed at 588 nm. Spectra were recorded and solid-phase media, identifying steric, kinetic, electronic and
every 30 s. Throughout this entire procedure, lights were kept off other micro-environmental factors. To facilitate incorporation of
and the UV-Vis spectrometer was covered with aluminium foil to the SP-MC molecular switch into novel micro-/nano-optoelec-
prevent any stray light causing unwanted photochemical rever- tronic devices, we have developed a means towards fine tuning of
sion of WR-MC / WR-SP. key elements; electronic and kinetic properties. Herein we have
described the synthesis of photochromic polymer microparticles
(4a and 4b) and studied the electronic and kinetic properties of
Thin film thermal reversion in solution, condensed and solid state media
with comparisons made with the unbound dye in the same media
Thin film samples were prepared by a blade-coating procedure
(1a and 1b).
that used blades from Paul N. Gardner Company, Inc. Film
UV-Vis analysis of the coloured MC (5a or 5b) within the
thickness was achieved using blades with pre-set heights,
microparticle points to a more polar environment than that in
measured in mils (1 mil ¼ 1/1000 th of an inch, ¼ 25.4 mm).
toluene, compared with the unbound dye, 604 (2a)/600 nm (2b)
A Mylar solid support was chosen for the fabrication of the thin
to 588 nm (5a and 5b). However, Reichardt’s dye and the cross-
films.
linked resin structure indicate unchanged polarity; rather it is
modification of the micro-environment in terms of spatial
confinement of the photochrome which is affected. The resulting
Preparation of thin film of 1a and 1b blue-shift in lmax is effected by restrictions imposed by the cross-
Thin films of SP were prepared by blade coating a mixture of SP linked polystyrene resin micro-environment surrounding the
(50 mg) in viscous toluene (2.5 ml) onto Mylar. The thickness of photochrome, precluding formation of the highly planar MC
the thin film samples was set at 5 mils (127 mm or 0.127 mm). form. Kinetics of thermal reversion were carried out for the
Films were left to air-dry overnight. unbound (2a and 2b) and resin-bound (5a and 5b) MCs
in solution, condensed and solid state media. A decrease in
MC / SP kobs was observed upon changing the micro-envi-
ronment from solution/condensed to solid state for both
Preparation of thin film of WR-SP
unbound and resin-bound dyes. Changes in kobs progressing
Thin films of WR-SP were prepared by blade coating a mixture from solution/condensed to solid state were larger for unbound
of WR-SP (200 mg) in viscous toluene (2.5 ml) onto Mylar. The than for resin-bound dyes, indicative of the importance played by
thickness of the thin film samples was set at 30 mils (762 mm or the micro-environment in determining kinetic properties of
0.762 mm). The film was then air dried for one hour before molecular switches.
a second coating of toluene (150 ml)/polystyrene (42 g, We have shown how modification of micro-environment for
Mw ¼ 70,000) solution with a 40 mils (1.016 mm) blade was a photochromic molecular switch can determine the fine-tuning
applied to smooth the film and refractive index match the resin of both electronic and kinetic properties. This highlights the need
and the film. Films were then left to air-dry overnight. for consideration of support systems for dye-incorporating

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 View Article Online

micro-/nano-optoelectronic devices, while at the same time SPIE-Proceedings (Organic Photonic Materials and Devices VII),
opening a window of opportunity to exploit further the electronic 2005, 5724, 13–20.
7 M. Tomasulo, S. L. Kaanumal, S. Sortino and F. M. Raymo, J. Org.
and kinetic properties without resorting to extreme measures. We Chem., 2007, 72, 595–605; A. Garcia, M. Marquez, T. Cai,
have also shown how consideration of particle size does not play R. Rosario, Z. Hu, D. Gust, M. Hayes, S. A. Vail and C.-D. Park,
a role in affecting either of these properties (electronic/kinetic), as Langmuir, 2007, 23, 224; I. Vlassiouk, C.-D. Park, S. A. Vail,
such making microparticle encased molecular switches ideal D. Gust and S. Smirnov, Nano Lett., 2006, 6, 1013; R. Rosario,
D. Gust, A. A. Garcia, M. Hayes, J. L. Taraci, T. Clement,
candidates for incorporation into optoelectronic devices. Further J. W. Dailey and S. T. Picraux, J. Phys. Chem. B, 2004, 108, 12640;
studies are proposed to deduce tethering chain length and resin M. Matsumoto, T. Nakazawa, V. A. Mallia, N. Tamaoki,
cross-linking effects on resin-confined dye molecules. R. Azumi, H. Sakai and M. Abe, J. Am. Chem. Soc., 2004, 126,
1006; Y. Einaga, M. Taguchi, G. Li, T. Akitsu, Z. Gu, T. Sugai and
Modification of the electronic properties for any dye molecule O. Sato, Chem. Mater., 2003, 15, 8; F. M. Raymo, R. J. Alvarado,
Published on 08 June 2010. Downloaded by Universidad de Oviedo on 27/10/2014 17:42:47.

can be a challenging process. While there is no doubt that S. Giordani and M. A. Cejas, J. Am. Chem. Soc., 2003, 125, 2361;
computational studies can aid in designing the ideal system prior F. M. Raymo, S. Giordani, A. J. P. White and D. J. Williams,
to chemical alteration, it can clearly be seen that implanting this J. Org. Chem., 2003, 68, 4158.
8 M. Tomasulo, S. Sorinto and F. M. Raymo, J. Photochem. Photobiol.,
new dye into varying support systems will have an impact. Here A, 2008, 200, 44–49.
we advocate a coupling of chemical modification (coarse tuning) 9 A. Tsuda, S. Sakamoto, K. Yamaguchi and T. Aida, J. Am. Chem.
with micro-environment (fine tuning) changes towards positively Soc., 2003, 125, 15722; J. H. Day, Chem. Rev., 1968, 68, 649.
10 N. Kobayashi, S. Miura, M. Nishimura and H. Urano, Sol. Energy
impacting on the desired electronic and kinetic properties of dye
Mater. Sol. Cells, 2008, 92, 136; M.-Y. Chou, M.-K. Leung,
molecules, thereby enabling achievement of tailored optoelec- Y. O. Su, C. L. Chiang, C.-C. Lin, J.-H. Liu, C.-K. Kuo and C.-
tronic devices. Y. Mou, Chem. Mater., 2004, 16, 654; D. M. DeLongchamp and
P. T. Hammond, Chem. Mater., 2004, 16, 4799.
11 W. Zhao and E. M. Carreira, J. Am. Chem. Soc., 2002, 124, 1582;
F. V€ ogtle, M. Gorka, R. Hesse, P. Ceroni, M. Maestri and
Acknowledgements V. Balzani, Photochem. Photobiol. Sci., 2002, 1, 45–51; A. Adronov
and J. M. J. Frechet, Chem. Commun., 2000, 1701; J. Anders,
The authors thank the Natural Sciences and Engineering H. J. Byrne, J. Poplawski, S. Roth, T. Bj€ ornholm, P. Sommer-
Research Council of Canada (EB) for funding this research. Larsen and K. Schaumburg, Synth. Met., 1993, 57, 4820; C. Bohne,
M. G. Fan, Z. J. Li, Y. C. Liang, J. Lusztyk and J. C. Scaiano,
J. Photochem. Photobiol., A, 1992, 66, 79; J. C. Scaiano, C. Chen
References and P. F. McGarry, J. Photochem. Photobiol., A, 1991, 62, 75.
12 I. Yildiz, E. Deniz and F. M. Raymo, Chem. Soc. Rev., 2009, 38,
1 G. Zou, H. Yang, M. Jain, H. Zhou, D. Williams, M. Zhou, 1859–1867; M. Tomasulo, E. Deniz, R. J. Alvarado and
T. McCleskey, A. Burrell and Q. Jia, Carbon, 2009, 47, 933–937; F. M. Raymo, J. Phys. Chem. C, 2008, 112, 8038–8045; G. Jiang,
E. S. Erickson, P. W. Livanec, J. F. Frisz and R. C. Dunn, Y. Song, X. Guo, D. Zhang and D. Zhu, Adv. Mater., 2008, 20,
Langmuir, 2009, 25, 5098–5102; T. Suga, S. Wi and T. E. Long, 2888–2898; A. Plaquet, M. Guillaume, B. Champagne, F. Castet,
Macromolecules, 2009, 42, 1526–1532; J. Ji, G. Sui, Y. Yu, Y. Liu, L. Ducasse, J.-L. Pozzo and V. Rodriguez, Phys. Chem. Chem.
Y. Lin, Z. Du, S. Ryu and X. Yang, J. Phys. Chem. C, 2009, 113, Phys., 2008, 10, 6223–6232; V. A. Barachevsky, J. Photochem.
4779–4785; S. Nouraei and S. Roy, Electrochim. Acta, 2009, 54, Photobiol., A, 2008, 196, 180–189.
2444–2449; J. Kouvetakis and A. V. G. Chizmeshya, J. Mater. 13 C. Tu, E. A. Osborne and A. Y. Louie, Tetrahedron, 2009, 65, 1241–
Chem., 2007, 17, 1649–1655. 1246.
2 P. A. Denis, R. Faccio and A. W. Mombru, ChemPhysChem, 2009, 14 S. Yagi, S. Nakamura, D. Watanabe and H. Nakazumi, Dyes Pigm.,
10, 715–722; S. Kim, S. Ju, J. Hee Back, Y. Xuan, P. D. Ye, 2009, 80, 98–105; F. Benito-Lopez, S. Scarmagnani, Z. Walsh,
M. Shim, D. B. Janes and S. Mohammadi, Adv. Mater., 2009, 21, B. Paull, M. Macka and D. Diamond, Sens. Actuators, B, 2009,
564–568; G. Zhang, W. Wang, Q. Yu and X. Li, Chem. Mater., 140, 295–303.
2009, 21, 969–974; S. W. Lee, A. Kornblit, D. Lopez, S. V. Rotkin, 15 D. Hu, Z. Tian, W. Wu, W. Wan and A. D. Q. Li, J. Am. Chem. Soc.,
A. A. Sirenko and H. Grebel, Nano Lett., 2009, 9, 1369–1373; 2008, 130, 15279–15281.
R. V. Ulijn and A. M. Smith, Chem. Soc. Rev., 2008, 37, 664–675; 16 S. M. Aldoshin, J. Photochem. Photobiol., A, 2008, 200, 19–33;
V. Georgakilas, D. Gournis, V. Tzitzios, L. Pasquato, D. M. Guldi K. Nakatani and P. Yu, Adv. Mater., 2001, 13, 1411–1413.
and M. Prato, J. Mater. Chem., 2007, 17, 2679–2694; P. Belser, 17 Z. Liu, L. Jiang, Z. Liang and Y. Gao, J. Mol. Struct., 2005, 737, 267;
L. De Cola, F. Hartl, V. Adamo, B. Bozic, Y. Chriqui, V. M. Iyer, X. Guo, Y. Zhou, D. Zhang, B. Yin, Z. Liu, C. Liu, Z. Lu, Y. Huang
R. T. F. Jukes, J. K€uhni, M. Querol, S. Roma and N. Salluce, Adv. and D. Zhu, J. Org. Chem., 2004, 69, 8924; K. Kimura,
Funct. Mater., 2006, 16, 195–208. M. Nakamura, H. Sakamoto, R. M. Uda, M. Sumida and
3 D. Abdallah, M. J. Cully, Y. Li and D. A. Shipp, Colloid Polym. Sci., M. Yokoyama, Bull. Chem. Soc. Jpn., 2003, 76, 209; A. Grofcsik,
2008, 286, 739; D. Abdallah, M. A. A. Ghani, M. F. Cunningham, P. Baranyai, I. Bitter, A. Gr€
un, E. K€
oszegi, M. Kubinyi, K. Pal and
P. M. Kazmaier, B. Keoshkerian and E. Buncel, Can. J. Chem., T. Vid oczy, J. Mol. Struct., 2002, 614, 69; A. M. A. Salhin,
2004, 82, 1393–1402; M. A. A. Ghani, D. Abdallah, M. Tanaka, K. Kamada, H. Ando, T. Ikeda, Y. Shibutani,
P. M. Kazmaier, B. Keoshkerian and E. Buncel, Can. J. Chem., S. Yajima, M. Nakamura and K. Kimura, Eur. J. Org. Chem.,
2004, 82, 1403–1412; A. Natansohn and P. Rochon, Chem. Rev., 2002, 655; Y. P. Strokach, O. A. Fedorova, S. P. Gromov,
2002, 102, 4139; A. Natansohn and P. Rochon, Adv. Mater., 1999, A. V. Koshkin, T. M. Valova, V. A. Barachevsky, M. V. Alfimov,
11, 1387; T. Hayashita, T. Kurosawa, T. Miyata, K. Tanaka and V. A. Lokshin, A. Samat and R. Guglielmetti, Russ. Chem. Bull.,
M. Igawa, Colloid Polym. Sci., 1994, 272, 1611; G. S. Kumar and 2002, 51, 58; K. Kimura, M. Sumida and M. Yokoyama, Chem.
D. C. Neckers, Chem. Rev., 1989, 89, 1915; N. Nishimura, Commun., 1997, 1417; A. Kellman, F. Tfibel, E. Pottier,
T. Sueyoshi, H. Yamanaka, E. Imai, S. Yamamoto and R. Guglielmetti, A. Samat and M. Rajzmann, J. Photochem.
S. Hasegawa, Bull. Chem. Soc. Jpn., 1976, 49, 1381. Photobiol., A, 1993, 76, 77.
4 C.-C. Ko, W.-M. Kwok, V. W.-W. Yam and D. L. Phillips, Chem.– 18 J. T. C. Wojtyk, A. Wasey, N.-N. Xiao, P. M. Kazmaier, S. Hoz,
Eur. J., 2006, 12, 5840–5848. C. Yu, R. P. Lemieux and E. Buncel, J. Phys. Chem. A, 2007, 111,
5 M. Siebold, H. Port and H. C. Wolf, Mol. Cryst. Liq. Cryst., 1996, 2511; Y. Zhou, D. Zhang, Y. Zhang, Y. Tang and D. Zhu, J. Org.
283, 75–80. Chem., 2005, 70, 6164; N. Xiao, Y. Chen, R. Lemieux, E. Buncel,
6 M. Suzuki, T. Asahi and H. Masuhara, J. Photochem. Photobiol., A, G. Iftime and P. M. Kazmaier, Mol. Cryst. Liq. Cryst., 2005, 431,
2006, 178, 170–176; R. Gvishi, Z. Kotler, G. Berkovic, P. Krief, 337; A. Fissi, O. Pieroni, N. Angelini and F. Lenci,
M. Sigalov, L. Shapiro, D. Huppert, L. V. Vladimir and A. Samat, Macromolecules, 1999, 32, 7116.

5734 | J. Mater. Chem., 2010, 20, 5727–5735 This journal is ª The Royal Society of Chemistry 2010
 View Article Online

19 J. T. C. Wojtyk, P. M. Kazmaier and E. Buncel, Chem. Mater., 2001, J. Locklin, Chem. Commun., 2008, (47), 6288–6290; O. Pieroni,
13, 2547; J. T. C. Wojtyk, E. Buncel and P. M. Kazmaier, Chem. A. Fissi, N. Angelini and F. Lenci, Acc. Chem. Res., 2001, 34, 9–17;
Commun., 1998, (16), 1703. A. Fissi, O. Pieroni, G. Ruggeri and F. Ciardelli, Macromolecules,
20 J. T. C. Wojtyk, A. Wasey, P. M. Kazmaier, S. Hoz and E. Buncel, 1995, 28, 302–309.
J. Phys. Chem. A, 2000, 104, 9046–9055. 29 L. Zhu, M.-Q. Zhu, J. K. Hurst and A. D. Q. Li, J. Am. Chem. Soc.,
21 X. L. Li, J. L. Li, Y. M. Wang, T. Matsuura and J. B. Meng, 2005, 127, 8968.
J. Photochem. Photobiol., A, 2004, 161, 201–213; G. Baillet, 30 M.-Q. Zhu, L. Zhu, J. J. Han, W. Wu, J. K. Hurst and A. D. Q. Li,
M. Campredon, R. Guglielmetti, G. Giusti and C. Aubert, J. Am. Chem. Soc., 2006, 128, 4303.
J. Photochem. Photobiol., A, 1994, 83, 147–151; G. Baillet, G. Giusti 31 J. Whelan, J. T. C. Wojtyk and E. Buncel, Chem. Mater., 2008, 20,
and R. Guglielmetti, J. Photochem. Photobiol., A, 1993, 70, 157–161. 3797–3799.
22 H. Gorner, Phys. Chem. Chem. Phys., 2001, 3, 416. 32 A. R. Vaino and K. D. Janda, J. Comb. Chem., 2000, 2, 579–596;
23 C. Salemi, G. Giusti and R. Guglielmetti, J. Photochem. Photobiol., A, A. W. Czarnik, Biotechnol. Bioeng., 1998, 61, 77;
1995, 86, 247; M. Sakuragi, K. Aoki, T. Tamaki and K. Ichimura, P. H. H. Hermkens, H. C. J. Ottenheijm and D. C. Rees,
Published on 08 June 2010. Downloaded by Universidad de Oviedo on 27/10/2014 17:42:47.

Bull. Chem. Soc. Jpn., 1990, 63, 74. Tetrahedron, 1997, 53, 5643–5678; F. Balkenhohl, C. Bussche-
24 H. Durr and H. Bouas-Laurent, Photochromism, Molecules and Hiinnefeld, A. Lansky and C. Zechel, Angew. Chem., Int. Ed. Engl.,
Systems in Studies in Organic Chemistry, Elsevier, Amsterdam, 1996, 35, 2288–2337; L. A. Thompson and J. A. Ellman, Chem.
2003; S. Kobatake and M. Irie, Annu. Rep. Prog. Chem., Sect. C, Rev., 1996, 96, 555–600; R. B. Merrifield, J. Am. Chem. Soc., 1963,
2003, 99, 277; G. Berkovic, V. Krongauz and V. Weiss, Chem. Rev., 85, 2149; B. A. Bunin and J. A. Ellman, J. Am. Chem. Soc., 1992,
2000, 100, 1741. 114, 10997; B. A. Bunin and J. A. Ellman, Proc. Natl. Acad. Sci.
25 M. Riskin, E. Katz, V. Gutkin and I. Willner, Langmuir, 2006, 22, U. S. A., 1994, 91, 4708.
10483; A. Doron, E. Katz, G. Tao and I. Willner, Langmuir, 1997, 33 A. Dahan and M. Portnoy, J. Am. Chem. Soc., 2007, 129, 5860;
13, 1783. P. Cristau, J.-P. Vors and J. Zhu, Tetrahedron Lett., 2003, 40, 7859;
26 Z. Tian, W. Wu and A. D. Q. Li, ChemPhysChem, 2009, 10, 2577; C. W. Phoon and M. M. Sim, J. Comb. Chem., 2002, 4, 491.
M. Piech, M. C. George, N. S. Bell and P. V. Braun, Langmuir, 34 M. Aizawa, K. Namba and S. Suzuki, Arch. Biochem. Biophys., 1977,
2006, 22, 1379; N. S. Bell and M. Piech, Langmuir, 2006, 22, 1420; 180, 41.
B. I. Ipe, S. Mahima and K. G. Thomas, J. Am. Chem. Soc., 2003, 35 J. Blas, A. Rivera-Sagredo, R. Ferritto and J. F. Espinosa, Magn.
125, 7174. Reson. Chem., 2004, 42, 950.
27 Z. Tian, W. Wu, W. Wan and A. D. Q. Li, J. Am. Chem. Soc., 2009, 36 R. Santini, M. C. Griffith and M. Qi, Tetrahedron Lett., 1998, 39,
131, 4245–4252. 8951–8954.
28 Z. Qiu, H. Yu, J. Li, Y. Wang and Y. Zhang, Chem. Commun., 2009, 37 C. Reichardt, Org. Process Res. Dev., 2007, 11, 105; C. Reichardt, in
3342; A. Radu, R. Byrne, N. Alhashimy, M. Fusaro, S. Scarmagnani Solvent and Solvent Effects in Organic Chemistry, Wiley-VCH,
and D. Diamond, J. Photochem. Photobiol., A, 2009, 206, 109–115; Weinheim, Germany, 3rd ed, 2003; S.-R. Keum, K.-B. Lee,
S. Samanta and J. Locklin, Langmuir, 2008, 24, 9558–9565; J. Chen, P. M. Kazmaier and E. Buncel, Tetrahedron Lett., 1994, 35, 1015;
F. Zeng, S. Wu, J. Zhao, Q. Chen and Z. Tong, Chem. Commun., S.-R. Keum, M.-S. Hur, P. M. Kazmaier and E. Buncel, Can. J.
2008, (43), 5580–5582; K. Fries, S. Samanta, S. Orski and Chem., 1991, 69, 1940.

This journal is ª The Royal Society of Chemistry 2010 J. Mater. Chem., 2010, 20, 5727–5735 | 5735