Synthesis and Layer-by-Layer Assembly of Water-Soluble

Chapter 24

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Synthesis and Layer-by-Layer Assembly of Water-Soluble Polyferrocenylsilane Polyelectrolytes *

Zhuo Wang, Geoffrey A . Ozin , and Ian Manners

*

Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada

Polyferrocenylsilanes (PFSs) are an interesting class of high molecular weight transition metal-containing polymers which exhibit attractive redox, semiconductive, preceramic and other physical properties. Convenient routes to a range of cationic and anionic water-soluble PFS polyelectrolytes have been achieved. These metal-containing materials are readily soluble in water and have been utilized in the self-assembly of multilayer superlattices. The electrostatic assembly of the water-soluble PFSs have also been used in tuning the optical properties of photonic crystals with nanometer scale precision.

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© 2006 American Chemical Society

Schubert et al.; Metal-Containing and Metallosupramolecular Polymers and Materials ACS Symposium Series; American Chemical Society: Washington, DC, 2006.

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Background Polyelectrolytes are a class of macromolecules which possess ionic groups along the polymer chains. Most of these macromolecules are water soluble and are of considerable importance to many industrial and technological applications . Polyelectrolytes have attracted intense interest since the early 1990's as the building blocks for electrostatic superlattices . These are multilayer structures that are assembled by sequential adsorption of oppositely charged polyelectrolyte monolayers from aqueous solutions. The resulting multilayers are nanometer-scale ultra thin films which have found wide applications in many areas . For example, the electrostatically assembled multilayers have been used successfully in surface property modifications and surface patterning, as well as in manufacturing of thin film devices and development of capsules for controlled drug releases . Interestingly, despite extensive studies, the polyelectrolytes used in the layer-by-layer assembly process are generally limited to organic macromolecules. To date examples of inorganic polyelectrolytes are rare. This is especially the case for transition metal-containing polymers, which would be expected to bring many attractive features, such as conductive, optical, redox, and catalytic properties, to the ultrathin multilayered films . 1

2,3


3

4

5,6

Polyferrocenylsilanes (PFSs) are a class of high molecular weight metalcontaining polymers with many interesting properties . These polymers are readily accessible via the thermal, anionic, transition metal-catalyzed, and most recently, photolytic anionic ring-opening polymerization (ROP) of strained silicon-bridged [ 1 Jferrocenophanes . 5

7,8

R

R'

η

The PFS materials have demonstrated reversible redox activity and semiconductivity after oxidation . Their ability to dissipate charge makes them attractive materials as radiation protective coatings . PFSs also provide access to molded networks which can be pyrolyzed to give nanostructured ceramic materials with tunable magnetic properties . For example, ceramic films, macroscopic shapes, and micrometer-scale patterned structures have been successfully generated by this means . The introduction of acetylene moieties 7

9

10

11,12


336 to the PFS has made it possible to incorporate a variety of other transition metals to the polymers . Highly metallized PFSs containing cobalt clusters have been synthesized and provide a route to both patterned and well-ordered 2dimentional nanostructures with interesting magnetic properties * . In addition, PFS block copolymers have been generated via anionic and transition metalcatalyzed R O P and form phase-separated domains in the solid state and selfassembled micellar aggregates in solution ' . Pyrolysis or plasma treatment of well-ordered PFS domains affords catalytically-active iron nanoclusters which can be utilized to generate carbon nanotubes . PFS materials also offer potential applications in microsphere technology , as photonic band gap materials , as variable refractive index sensing materials and as etch resists . 13,14

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Objective Organometallic superlattices formed by layer-by-layer electrostatic assembly o f PFS polyelectrolytes are of great interest and expected to provide novel properties. The objectives of this study were to synthesize both cationically and anionically charged water-soluble PFSs, assemble organicorganometallic and all organometallic electrostatic superlattices on various substrates, and study the assembly behavior of the polyelectrolytes.

Experimental A l l chemicals were purchased from Aldrich and used as received unless otherwise specified. (3-Aminopropyl)trimethoxysilane was purchased from Gelest Inc.. Polymer [fcSiMeCl]* (l) , fcSiMeCl (3), fcSiMe(2-C H CH NMe ) (4) , and L i C = C C H N ( S i M e C H ) (6) were synthesized according to literature procedures. N M R characterizations and molecular weight determinations were carried out as previously described " . The concentrations of the polyelectrolyte solutions were 10 m M PSS and 10 m M PFS in 0.1 M NaCl aqueous solutions. The preparation o f Si and A u substrates and the layer-by-layer assembly of polyelectrolytes was carried out as previously described . Quartz crystal microbalance (QCM) measurement data, ellipsometric data, UV-vis spectra of quartz-supported PSS-PFS films, X-ray photoelectron spectra, and advancing contact angles for water were obtained as previously described . 26

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2

2

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Results & Discussion Synthesis of the Cationic P F S Polyelectrolytes The first water-soluble PFS was prepared via nucleophilic reactions on poly(ferrocenylmethylchlorosilane) 1 with alkoxide that possess dimethylamino functional groups (Scheme l ) . quaternization of the amino groups with methyl iodide afforded polymer 2. 2 9

substitution nucleophiles Subsequent the cationic -NMe I


3

Scheme 1. (i) HOCH CH NMe , 2

2

2

Et N, toluene, 25°C (ii) Mel CH Cl , reflux. 3

2

2

Another synthetic route to water-soluble cationic PFS is via thermal ringopening polymerization of monomer 4 which was generated from fcSiMeCI (3) via substitution of the chloride with an aryl lithium reagent (Scheme 2 ) . 27,34

Scheme 2. (i) 2-C H CH NMe Li, Me£0 , 6

4

2

2

4

THF, -78 °C (ii) Xylene, 160 °C, 16 h. (iii) CH Cl , 25 °C, 24 h. 2

2


338 Quaternization of the amino groups in the resulting polymer with dimethyl sulfate afforded the cationic polymer 5 (Scheme 2) . Complete reaction was confirmed by H , C and S i N M R in both D 0 and deuterated D M S O . The cationic polyferrocenylsilanes were also envisioned to arise from the protected aminoalkynyl PFS 7 . It was expected that, upon silyl group removal, polymer 7 would function as a precursor to PFS polyelectrolytes via quaternization and other derivatization methods. PFS 7 was readily accessible through nucleophilic substitution of the chlorine atoms on poly(ferrocenylmethylchlorosilane) l with a lithium acetylide reagent (6) (Scheme 3 ) . The lithium acetylide 6 was prepared in situ from H C = C C H N ( S i M e C H ) - and w-BuLi. Complete substitution of the chlorine side groups of 1 was confirmed by H , C and S i N M R . G P C analysis of polymer 7 showed that the material possessed a molecular weight of A / = 304,100 and a PDI = 1.48. Subsequent removal of the cyclic disilyl protecting groups was achieved under mild conditions in a mixture of THF+MeOH solvents (3:1 v/v) to give the aminopropynyl PFS 8. Further reduction of 9 with hydrazine under air afforded polymer 9. 30

!

l 3

2 9

2

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2

6

28,35

28

2

2

2

36

2


!

l 3

2 9

w

CI Me (·)

7 R -(SiMejCH )2 2

2

Scheme 3. (i) LiC=CCH N(SiMe CHi) (6), THF, 0 to 25 °C. (ii) THF + MeOH, 25 °C, 4 days, (iii) Hydrazine, THF, 25 °C. 2

2

2


339 Alternatively, PFS 7 can be prepared via catalytic ROP of monomer 10, which was derived from fcSiMeCl (3) via nucleophilic substitution reaction with L i C = C C H N ( S i M e C H ) (6) (Scheme 4) . 28


2

2

2

2

PFS 11 and 12 with quaternary ammonium substituents were readily obtained through protonation of the amino polymers 8 and 9, respectively, with 1 equiv of HC1 (1 M solution in ether) (Figure 1). Both cationic polymers were

Figure L Cationic PFS polyelectrolytes 11 and 12.


340 very soluble in water and their solutions remained clear orange-yellow over a period of several months.

Synthesis of Anionic PFS Polyelectrolytes The synthesis of anionic PFSs was achieved using the reaction of the polymer 7 with 1,3-propane sultone in the presence of an excess amount of diisopropylethylamine in a mixture of solvents (THF+MeOH, 2:1 v/v) (Scheme 5). Precipitation of the crude product into an acetone solution containing sodium hexafluorophosphate or sodium tetraphenylborate for cation-exchange purposes afforded polymer 13 as an orange-yellow powder in high yield (>90%). Subsequent reduction of 13 with hydrazine yielded PFS 14. Both anionic polymers were yellow powders, highly soluble in water, and remained stable in water after a period of several months.


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Scheme 5. (i) 1,3-propane sultone, (i-Pr) EtN THF + MeOH, 25 °C (ii) Hydrazine, H O 25 °C. 2

2

9

t


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Layer-by-Layer Assembly of Organic-Organometallic and A l l Organometallic Polymer Superlattices The assembly of the electrostatic superlattices was accomplished by the alternate adsorption of the anionic and cationic polyelectrolytes on Si and A u substrates that have been chemically modified with (3-aminopropyl) trimethoxysilane (APMS) and 2-aminoethanethiol (AET), respectively . In the following discussion, the organic-organometallic PSS-PFS multilayer films were assembled from the anionic poly(styrenesulfonate) (PSS) and cationic PFS 5, while the all organometallic PFS-PFS multilayers were assembled from the anionic polyelectrolytes PFS 14 and cationic PFS 5 . A schematic representation of the sequential adsorption process is shown in Figure 2. The L b L assembly of the organic-organometallic polymer superlattices was monitored using a Q C M derivatized with A E T . The measurement of the frequency change of a 10 M H z Q C M was plotted against the number of bilayers deposited on the substrate (Figure 3a). A slight nonlinearity was observed in the initial three deposition steps. This is probably due to the initial substrate priming step or the L b L adsorption behavior of the polyelectrolytes in the early dipping steps. After the initial steps, a linear growth of the multilayers was observed. The increase of film thickness on both Si and A u substrates during the assembly process was observed by using ellipsometry measurements (Figure 3b) . The nearly superimposable curves for films grown on both substrates suggest that the growth pattern of the films is independent of the substrates. The average growth of thickness for each PSS and PFS layer is 7 ± 3 Â and 16 ± 5 Â, respectively. The thicker layer of the latter is attributed to its lower charge density, therefore a larger amount of the PFS polyelectrolyte is needed to compensate for the surface charges of the PSS layer. The linear sequential buildup of the PSS-PFS superlattices on quartz substrates was followed by UV-vis spectroscopy (Figure 4 ) . The characteristic absorptions of PFS are centered at 220 nm, an intense ligand-to-metal chargetransfer transition ( L M C T ) , and at 450 nm, a much weaker d - d transition in the visible region. The PSS π - π* transition is centered at 260 nm. The absorbances at 220 nm, 260 nm and 450 nm increased linearly with the increase of the bilayer number. This indicates a regular increase of adsorbed polymer with each deposition step. The linear relationship between the superlattice absorbance and the deposition layer number was again observed for the all organometallic PFS-PFS superlattice on quartz (Figure 5) . These UV-vis results, in conjunction with the Q C M and ellipsometry data, support the proposed L b L assembly of electrostatic superlattices as illustrated schematically in Figure 2. The surface composition of the PSS-PFS films grown on A u substrates was measured by X P S . For the film composed of 10 layers of polyelectrolytes, the photoelectron spectrum measured at take-off angle 90° was compared to the 32


3 2 , 3 3

3 2

32

3 2

33

32



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Figure 2. Schematic representation ofsequential polymer electrolyte adsorption for growing PSS-PFS organic-organometallic multilayer thin films. (Reproduced with permission from reference 32.)



Figure 3. Layer-by-layer electrostatic superlattice assembly, (a) QCM data for the growth of PSS-PFS multilayer films, (b) Ellipsometric film thickness as a function of layer number on silicon (J and gold (- - -) substrates. (Reproduced with permission from reference 32.)


Schubert et al.; Metal-Containing and Metallosupramolecular Polymers and Materials ACS Symposium Series; American Chemical Society: Washington, DC, 2006. Wavelength (nm)

Figure 4. UV-vis spectra for PSS-PFS thin films corresponding to 2, 4, 6, 8, 10, 12, and 14 bilayers. (a) Region showing the PFS LMCT at 220 nm and the π - τ τ * transition at 260 nm. (b) Scale-expanded spectra showing the PFS d-d transition at 450 nm. Insets show the systematic increase in absorbance with bilayer number at (a) 220 run (J, 260 nm (- - -), and (b) 450 nm. The different slopes in the inset of (a) result from the different molar absorbances of PFS at the corresponding wavelengths. (Reproduced with permission from reference 32.)

Wavelength (nm)



(a)

a

S

200

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τ

Wavelength (nm)

400

500

600 300

400 500 Wavelength (nm)

600

Figure 5. UV-vis spectrafor PFS-PFS multilayers corresponding to layers 1 to 10. (a) Region of the UV-vis spectra showing the PFS LMCT at - 220 nm. (b) Scale-expanded spectra showing the PFS d-d transition at ~- 420 nm. Insets show the systematic increase in absorbance with layer number at (a) 220 nm and (b) 420 nm. (Reproduced with permission from reference 33.)

1.05


347 spectrum measured at take-off angle 20°. In the latter case, while peaks for C, N , O, S, and Fe, which are present at the surface, are clearly observed, the A u peaks are greatly reduced in comparison to the spectrum measured at take-off angle 90°. This result indicates that the A u surface is essentially completely covered by the 10 layer film. The magnified Fe (2p) and S (Is) regions for the films composed of 6 and 10 layers illustrate the expected increase in relative intensity with the increase in layer buildup. The wettability properties of A u surfaces modified with the PSS-PFS layers were examined by using the advancing water contact angles measurements (Figure 6) . With the exception of the first PSS monolayer adsorbed on an A E T primed gold surface which gave an advancing water contact angle of 55° ± 2 ° , the advancing contact angle systematically alternates between 75° ± 2° for PSSterminated surfaces and 67° ± 5° for PFS-terminated surfaces. The consistent observation that the PFS-terminated surfaces have smaller advancing contact angle in comparison to the PSS-terminated surfaces indicates that the former are slightly more hydrophilic than the latter. These results also demonstrate that the wettability o f surfaces can be simply tuned by altering the outermost surface layer of the multilayer assembly . 32


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80 m

50 J

,

2

,

,

4 6 Layer number

.

8

r-

10

Figure 6. Advancing water contact angle on PSS (odd numbered layers) and PFSfeven numbered layers)-terminated multilayerfilms grown on Au substrates. (Reproduced from reference 32 with permission.)

The topography of the PSS-PFS film composed of 10 layers of polyelectrolyte on a A u substrate was examined by A F M (Figure 7) . The distribution of grain sizes in the gold-supported fnultilayers is 2000 - 10000 nm , larger than the gold globules for the bare substrate surface (distribution of grain sizes: 450 - 2000 nm ). This indicates a smoothing of the A u substrate surface. In addition, the root-mean-square (rms) roughness values measured for 32

2

2


348 the 10 layer film and the bare gold substrate were 6 and 9 Â, respectively, over a 500 nm scanned area. The minor variation in the surface topography and the rms roughness between the bare substrate surface and the PSS-PFS-deposited surface indicates that the growth of the multilayers follows the substrate surface morphology. The data from Q C M , ellipsometry, UV-vis, X P S , contact angle and A F M measurements of the PSS-PFS and PFS-PFS multilayers demonstrate that L b L assembly of oppositely charged metal-containing polyelectrolytes creates regularly stacked, homogeneous electrostatic superlattices with essentially complete surface coverage . 2


32

Direct Visualization of PSS-PFS and P F S - P F S Multilayers The electrostatically assembled multilayers can be directly visualized by using a gold coating/transmission electron microscopy ( T E M ) technique . Multilayers of PSS-PFS were formed through L b L assembly on a gold substrate. Once the deposition was complete, a thin layer of gold was sputtered on top of the film. As there is no intrinsic electronic contrast between the multilayer and surrounding medium, the gold substrate and top sputtered layer provide the contrast needed for T E M visualization. The cross-section images of the multilayer films consisting of 5, 10, 20, and 30 bilayers of alternating PFS and PSS are shown in Figure 8 . The uneven coverage of the first several multilayers can be clearly seen in the 5 and 10 bilayer superlattices. The regular increase in multilayer thickness can be visually followed in the preparation of films composed of 20 and 30 bilayers. 33

33

The effect of charge density of the polyelectrolytes on superlattice thickness was also investigated by using the direct visualization technique . A multilayer film composed of 20 bilayers of PSS-PFS was compared to that of 20 bilayers of PFS-PFS (Figure 9) . As PSS contains the single negative charge per repeat unit in a smaller volume than the anionic PFS, less PSS was required to compensate the positive charges in the underlying layer, which ultimately resulted in a thinner PSS-PFS film in comparison to the PFS-PFS film. 33

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L b L Assembly of P F S Polyelectrolytes in Silica Colloidal Crystals A n interesting application of the L b L assembly of PFS polyelectrolytes is in tuning the properties of photonic crystals at nanometer scale precision . Photonic crystals are a class o f materials which possess periodic variations in dielectric constants . Because of the photonic band gaps existed in these materials, photons having energy within the band gap are not transmitted through. Photonic crystals are a powerful tool for the manipulation of light and are building blocks for devices in optical communications . 39

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Schubert et al.; Metal-Containing and Metallosupramolecular Polymers and Materials ACS Symposium Series; American Chemical Society: Washington, DC, 2006. 2

Figure 7. Tapping-mode AFM images of (a) a bare gold substrate and (b) a 10 layer PFS-terminated film over a 500 nm area. (Reproduced with permission from reference 32.)



350

Figure 8. TEM images for (a) J, (b) 10, (c) 20, (d) 30 bilayerfilmsofPFS-PSS. (Reproduced with permissionfromreference 33.)

Figure 9. TEM images for 20 bilayers of (a) PSS-PFS and (b) PFS-PFS showing the effect of charge density on layer thickness. (Reproduced with permission from reference 33.)


351 The photonic crystals used in our study are 3-D ordered arrays of monodisperse silica colloidal spheres. The cationic and anionic PFS polyelectrolytes were alternately infiltrated in the opal structure, gradually filling the air voids with each step of deposition. The variation of the colloidal photonic crystal properties with the degree of polymer infiltration was monitored by optical transmission measurements, carried out by using a UV-vis spectrometer. As the number of deposition cycles increases, there is a gradual shift of the stop band peak to the longer wavelengths (Figure 10a, b) . This is in accordance with the spectra obtained from theoretical fittings using a scalar wave approximation (SWA) approach.


39

Figure 10. Experimental (a) and theoretical (b) optical spectra for a silica colloidal crystal film infiltrated of PFS-PFS. In (a), the corresponding number of deposition cycles increases from top to bottom by an increment of one bilayer between each curve, (c) Cross-sectional SEMof a silica-electrostatic multilayer composite colloidal photonic crystal. The inset displays a detail of the most external sphere layer, which is covered by a polymer layer. (Reproduced from reference 39 with permission.)

After a certain number of deposition cycles, a new peak starts to appear, blue-shifted relative to the original stop band peak frequencies. Theoretical simulations indicate that this is probably the result of an external layer deposited on top of the photonic crystal (Figure 10c) . The results of this work have demonstrated that electrostatic assembly of polyelectrolytes occurs on the internal and external surfaces of a colloidal crystal film and provides a powerful tool in tuning the optical properties of the photonic lattice with nanometer scale precision. 39


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Conclusions Facile syntheses of a range of water-soluble PFS polyelectrolytes have been achieved. Direct nucleophilic substitution reactions with the chlorinated PFS 1 by dimethylaminoalkyl alcohol followed by quaternization of the dimethylamino groups afforded the cationic PFS 2. Alternatively, ROP of [l]ferrocenophane 4 followed by quaternization of the amino groups gave the cationic PFS 5. In addition, nucleophilic substitution of the chlorine atoms on PFS 1 by lithium acetylide LiC=CCH N(SiMe CH )2 (6) provided an intermediate PFS 7, which can serve as a precursor to both the cationic PFSs 11 and 12 as well as the anionic PFSs 13 and 14. Downloaded by GEORGE MASON UNIV on October 6, 2016 | http://pubs.acs.org Publication Date: March 23, 2006 | doi: 10.1021/bk-2006-0928.ch024

2

2

2

Both the organic-organometallic PSS-PFS and the novel all organometallic PFS-PFS ultra thin films have been formed through the electrostatic assembly of the oppositely charged polyelectrolytes. The data from Q C M , ellipsometry, U V vis, X P S , contact angle and A F M measurements of the PSS-PFS and PFS-PFS multilayers demonstrate that L b L assembly of oppositely charged metalcontaining polyelectrolytes creates regularly stacked, homogeneous electrostatic superlattices with essentially complete surface coverage. And the electrostatically assembled ultra thin multilayers can be directly visualized by using a gold coating/transmission electron microscopy (TEM) technique. We have also demonstrated that the electrostatic assembly of polyelectrolytes provides a powerful tool in tuning the optical properties of the photonic lattice with nanometer scale precision.

Acknowledgments We acknowledge coworkers Madlen Ginzburg, Josie Galloro, Andre Arsenault, and John Halfyard and we thank the Natural Science and Engineering Research Council (NSERC) of Canada for funding. I M and G A O thank the Canadian Government for Canada Research Chairs.

References 1.

2.

See, for example: (a) Water-Soluble Polymers: Synthesis, Solution Properties and Applications; eds. Shalaby, S. W., Butler, G . B . , McCormick, C. L . ; A C S Symposium Series 467; American Chemical Society: Washington, D C , 1991. (b) Controlled Drug Delivery: Designing Technologies for the Future, eds. Park, K . , Mrsny, R. J.; A C S Symposium Series 7S2; American Chemical Society: Washington, D C , 2000. (a) Decher, G . Science 1997, 277, 1232. (b) Bertrand, P.; Jonas, Α.; Laschewsky, Α.; Legras, R. Macromol. Rapid Commun. 2000, 21, 319.


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7. 8. 9.

10. 11.

12. 13. 14. 15.

16.

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