Preparation of Functional Hybrid Glass Material from Platinum (II) Complexes for Broadband Nonlinear...

FULLPAPER

www.afm-journal.de

Preparation of Functional Hybrid Glass Material fromPlatinum (II) Complexes for Broadband NonlinearAbsorption of Light

By Roman Zieba, Cedric Desroches, Frederic Chaput, Marcus Carlsson,

Bertil Eliasson*, Cesar Lopes, Mikael Lindgren, and Stephane Parola*

The synthesis of trans-di(arylalkynyl)diphosphine platinum(II) complexes

bearing trialkoxysilane groups is described, as well as the preparation of

siloxane-based hybrid materials from organometallic chromophores through

a modified sol–gel process. Glass materials prepared from trans-[P(n–

Bu)3]2Pt[(C�C–p–C6H4–C�C–p–C6H4–CH2O(CO)NH(CH2)3Si(OC2H5)3]2generally show spectral transmittance, absorption and luminescence similar

to that of solutions reported in the literature. Measurements of optical power

limiting for the hybrid glass are carried out, and show broadband nonlinear

absorption throughout the whole visible wavelength range with clamping

values in the range 0.2–7mmJ at 120mM chromophore concentration. The sol–

gel process using urethane-propyltriethoxysilane-functionalized

chromophores as precursors appears to be a valid method for formation of

mplexes for OPL

1. Introduction

robust silicate materials with grafted diarylethynyl Pt(II) co

devices.

We are interested in the fundamental processes behind opticalpower limiting (OPL) and the development of nonlinear optical(NLO) materials for protection of optical sensors against laserlight.[1,2] It is well established that the mechanism termedreversible saturable absorption (RSA) can provide efficient

[*] Dr. B. Eliasson, Dr. M. CarlssonDepartment of ChemistryUmea University, Umea SE-901 87 (Sweden)E-mail: [email protected]

Prof. S. Parola, Dr. R. Zieba, Dr. C. Desroches, Dr. F. ChaputLaboratoire des Multimateriaux et Interfaces CNRS 5615University Claude Bernard Lyon 1University of Lyon, Villeurbanne 69622 (France)E-mail: [email protected]

Dr. C. LopesDep. of Optronic SystemsSwedish Defence Research Agency (FOI)Linkoping SE-581 11 (Sweden)

Prof. M. LindgrenDepartment of PhysicsNorwegian University of Science and TechnologyTrondheim NO-7491 (Norway)

DOI: 10.1002/adfm.200801008

Adv. Funct. Mater. 2009, 19, 235–241 � 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinh

limiting of pulsed laser irradiance.[3,4] RSAtypically can appear for molecular systemswith a non-negligible intersystem crossingand subsequent lifetime of an excitedtriplet (T1) state, comparable to or longerthan the duration of the laser pulse, andwith a substantial absorption coefficient ofthe T1 state compared to that of the groundstate. Another process that can contributeto OPL, especially for very short laserpulses, is two-photon absorption (TPA).[5–9]

In addition to the goal of a better under-standing of mechanisms for nonlinearabsorption for improved design of efficientOPL molecules and preparation of solidmaterials thereof, we anticipate that knowl-edge of such materials preparation couldalso be utilized in other photonic applica-tion areas.

The molecular engineering required for
the OPL function is essentially based on the presence of extendedp-electron systems. Insertion of a heavy metal atom that providesspin-orbit coupling enhances intersystem crossing (ISC) froman excited singlet state to a triplet state, which can lead to anenhancement of the optical limiting effect. An example of anorganometallic system in which the heavy atom facilitates ISCis the platinum(II) square-planar complex trans-[P(n–Bu)3]2Pt[(C�C–p–C6H4–C�C–p–C6H5]2 (1a, Fig. 1).[5,10,11] Complex 1ahas been extensively studied in solution for its nonlinearabsorption properties,[5,10–12] and we have recently preparedseveral related molecules with repeating arylethynyl groups intrans configuration for comparisons with 1a.[13–17] The solutionOPL studies of platinum polymeric structures have also beenreported recently.[18–20] The solutions of the compounds (usuallyin tetrahydrofuran) show good OPL properties and are fairlytransparent in the visible region. However, to utilize the OPLmolecular functions in applications it is required that thechromophores can be introduced to and covalently connected to asolid optical host material that enables polishing and other post-processing. Although several papers deal with OPL studies insolution of a large variety of chromophores including platinumbased species, reports on preparation and properties of solid OPLmaterials are sparse. Moreover, the properties and behavior of thedyes in such solids still remains to be further investigated. Theideal matrix should have high optical quality and high damage
eim 235

FULLPAPER

www.afm-journal.de

Figure 1. Examples of structures of Pt(II) chromophores for solution studies (1a–2a) and

alkoxysilane functionalized chromophores (1b–2b) for organic-inorganic hybrid glass prep-

aration.

236

threshold under laser exposure. Inorganic materials, such assilica based systems used in optical glasses, are promisingcandidates for constituting such matrices. It is now wellestablished that the sol–gel process provides an interestinglow-temperature route to silica-based hybrid material for opticalapplications.[21] Although this approach seems both widely usedand promising, very few articles report on attempts to preparesuch OPL hybrid materials.[22]

A popular method for preparing a solid network is to eithersimply disperse, or embed with strong chemical bonds, theorganic dye in a SiO2 basedmatrix using the sol–gel technique.[23]

A disadvantage of this simple doping method is that the solubilityof the organic or organometallic chromophore is often low in themore polar Si-based component. Hence, chemical bonding of theorganics to the silicate can be preferable, especially forapplications where chromophore concentrations in the glass inthe range of 0.1–0.5 M or higher may be needed. The bonding canbe accomplished via tri-alkoxysilyl groups in the organicmolecular framework, which are hydrolysed and subsequentlyco-condensed with the silicon alkoxide during the sol–gelprocess.[24,25] In this approach, the Si-alkoxide and organiccomponents can bemixed in widely different ratios without phaseseparation, leading to so-called hybrid organic-inorganic nano-composites. Silica is expected to be a good choice ofmatrix since it

Scheme 1. Synthesis of Pt(II) chromophores 1b and 2b for sol–gel preparation of monolithic

glass materials.

combines high optical quality with good thermaland mechanical properties. Here, platinum(II)acetylide based OPL materials in sol–gel glassesare reported. The results will be compared withrecently reported results on similar molecularfunctions introduced into PMMA matrices.[26]

2. Results and Discussion

Here, we describe the syntheses of di(arylethynyl)-diphosphine Pt(II) complexes functionalized withsiloxane groups on the peripheral aromatic rings,1b–2b (Fig. 1). The sol–gel method has beenapplied for two-point attachment of the functio-nalized complexes to the SiO2 matrix. Results ofbasic spectroscopic characterization and OPLmeasurements on the prepared monolithicmaterials are also reported.

2.1. Synthesis of Pt(II) Compounds and

Preparation of Hybrid Monolithic Materials

On the basis of results from earlier OPL andphotophysical studies on platinum complexes in

� 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

solution, we selected compounds 1a and themethoxy-substituted analogue 2a for derivati-zation with triethoxysilane groups. The routesfor preparation of 1b–2b are outlined inScheme 1, and details are given in theexperimental section. The alkynes used asligands in the Pt(II) complexes were synthe-sized using a common strategy of Sonogashiracoupling between an alkyne and an aryl halide.Appropriate protecting groups were applied asneeded. The preparation of the organo-Pt(II)

precursors for sol–gel glass formation involved CuI-catalysedcoupling of a hydroxymethyl-substituted alkyne to trans-PtCl2(n–Bu3)2 in tetrahydrofuran (THF) and triethylamine (TEA). Thefinal step was the formation of the urethane link, by reaction ofthe organo-Pt alcohol and isocyanato propyltriethoxysilane(ICTES).

The method for the preparation of the hybrid monolithsinvolved acidic hydrolysis and polycondensation of methyl-triethoxysilane (MTEOS) and the organometallic compounddissolved in THF, followed by gel aging and drying to form a so-called xerogel. Some details of importance will be discussed later(neutralization of the sol, hydrolysis and condensation of thechromophore). The ageing time prior to drying is a crucial stepand varies depending on the procedure. At the beginning of thecondensation step, the added chromophore tends to precipitate ifthe solvent is removed too quickly since, at this point, aninsufficient number of links with the matrix network have beengenerated. The end of the aging course (condensation) wasestimated from the stage when no more precipitation wasobserved while drying a drop of the gel. At this instant theindividual chromophores are completely interconnected with thematrix and the gel could be shaped and dried without showingany precipitation. The xerogels were then dried using tempera-tures ranging from 70 to 120 8C to give the final monoliths. The

Adv. Funct. Mater. 2009, 19, 235–241

FULLPAPER

www.afm-journal.de

Figure 2. Example of hybrid organic-inorganic glass filters prepared from

sol-gel hybrid monoliths and used for OPL measurements.

Figure 4. DSCmeasurements of hybridmonoliths with a) in situ hydrolysis

and b) ex situ hydrolysis.

hybrid materials prepared for further photo-physical studies wereapproximately 3 cm in diameter and 4mm in thickness andcompletely homogeneous and free of cracks. They were cut andpolished to a final thickness of approximately 1.4mm (Fig. 2).Monoliths of larger diameter and thickness can be preparedfollowing the same procedure. BET-isotherm and thermopor-osimetry measurements were conducted on the materials and nomesoporosity could be detected.

2.2. Study of the Hydrolysis/Condensation Conditions

The hybrid monoliths can be prepared in several differentmanners. One process parameter is the way the chromophore ishydrolyzed, typically in situ with the matrix or following a two-step procedure with separate pre-hydrolysis of the chromophoreand co-condensation with the matrix in a second step (Fig. 3).Following our experimental conditions we observed a strongdecrease in the condensation time when the matrix and the dyeare hydrolyzed separately and then mixed together; froma) 20 days for procedure to b) 5 days for procedure. However,we could not observe any nonlinear optical response with the

Figure 3. Schematic procedures for the preparation of the hybrid mono-

liths with a) in situ hydrolysis and b) ex situ hydrolysis.

Adv. Funct. Mater. 2009, 19, 235–241 � 2009 WILEY-VCH Verl

materials prepared following procedure (b), while the propertieswere not completely recovered when using procedure (a). Onehypothesis is that the chromophores started to co-condensateprior to dispersion in the matrix network resulting in theformation of small aggregates. Thus, the interactions betweenthe proximate chromophores in the aggregates could quench theluminescence and the nonlinear absorption process. In the caseof procedure (b), differential scanning calorimetry (DSC)experiments showed a strong peak at 158 8C, which can beattributed to the melting point of the chromophore (Fig. 4). Thisconfirms the presence of aggregated chromophores in the matrixfrom method (b), in contrast to the materials prepared throughprocedure (a), where the chromophore was perfectly dispersedand no melting thus could be observed. However, the change inoptical properties such as phosphorescence in material (a) couldnot be explained, but will be discussed further below.

Other process parameters that were investigated were the pHand the catalyst, which is of special importance if thechromophore is sensitive to pH changes and the presence ofhydrochloric acid. Therefore, we prepared materials payingparticular attention to pH conditions. Thus, neutralization usingAPTES (3-aminopropyltriethoxysilane) was done prior to additionof the chromophore. Subsequently, the chromophore was slowlyhydrolyzed using diluted acidic water which was slowly added tothe mixture. Following this third procedure (Fig. 5), the agingtime was intermediate (7 days), compared to the two previousprocesses, prior to removal of the remaining solvents. Thesematerials were used for spectroscopic and OPL measurementsafter optical polishing. The optical results are discussed in Section2.3. Solid state 31P NMRwas conducted in order to check the final

Figure 5. Schematic procedure for the preparation of hybrid monoliths at

neutral pH (procedure c).

ag GmbH & Co. KGaA, Weinheim 237

FULLPAPER

www.afm-journal.de

18.4239

11.0350

4.0375

(ppm)-200-180-160-140-120-100-80-60-40-20020406080100120140160

58.7449

18.5707

11.8179

3.8907

(ppm)-200-180-160-140-120-100-80-60-40-20020406080100120140160

Figure 6. Solid state 31P NMR spectra of the hybrid monoliths prepared

from HCl catalyzed precursors (top) showing partial disruption of the

complex in the presence of HCl, and the signal of the pure chromophore 1b

in the matrix prepared avoiding contact between the chromophore and the

acid (bottom).

Figure 7. Linear transmission of a hybrid monolith with 90mM 1b (dotted

line) and a pure glass without chromophore (dashed line). Both samples

were prepared through the same sol–gel procedure.

238

quality of the chromophore in the material (Fig. 6). In the case ofprocedure (c), the spectrum shows only showed the signal of thephosphorus belonging to chromophore 1b at 11.8 ppm. On theother hand, spectra of the material prepared from procedure(a) display the signal of the chromophore and an additional peakat 57.8 ppm, which can be assigned to phosphorus oxide. Thisindicates that partial disruption of the chromophore occurredwhen the precursors were exposed to hydrochloric acid during thecatalysis step. When neutral conditions or other acids (forexample acetic acid) were used for the hydrolysis, thechromophore was preserved as well as the optical properties tobe further discussed below.

Hybrid monoliths of various concentrations were obtainedfrom 1b and were subjected to further investigations. The glasseshad sufficient strength to allow cutting and optical polishing.

2.3. Spectroscopic and OPL Characterization of Hybrid

Materials

A glass made from chromophore 1b with a concentration ofapproximately 40mM of the chromophore showed good transpar-ency in the visible region, with a transmittance (T) of 78% at the

� 2009 WILEY-VCH Verlag GmbH

common laser wavelength 532 nm. A corresponding glass withthe chromophore concentration of approximately 90mM hadT¼ 56% (Fig. 7). Here the transmission of the doped hybrid glassis compared to the case of a pure glass without organicchromophore component, both samples of approximately thesame thickness of 1.4mm. The measured refractive index of themonoliths was 1.43.

1b in THF solution has lmax¼ 357 nm and "¼ 9.7 �104M�1 cm�1 in the range of 300–800 nm. Emission spectraof the hybrid glass 1b were acquired using a ms flashlamp asexcitation. This experiment revealed emissions in accord with thatof 1a in solution,[5,13,15–17,27] in the region of 400–450nm and 500–600nm, as expected for fluorescence and phosphorescence,respectively (Fig. 8). An excitation spectrum was also obtained,while monitoring the emission at 520nm (Fig. 8). This showedseveral absorptions in the region of 350–500nmwhich result in thephosphorescence at 520nm. The bands at 356 and 380nm are dueto singlet-singlet excitation, whereas the bands at 455 and 485nmare due to direct forbidden excitation to triplet states. The latter arenormally very weak in absorption measurements but becomeenhanced using the excitation mode of detection. Time-resolvedemissionmeasurements were carried out using an up-converted fsTi:Sapphire laser at 356nm, set to low repetition rate using a pulsepicker [See Ref. [17] for details on set-up]. Generally, thefluorescence band in the range 380–520 decayed too fast to becharacterized using our setup (< 50ps). The mono-exponentialdecay upon excitation at 356nm and monitoring the emission at520nm gave a decay trace as in Figure 8b. This could be fitted to aphosphorescence decay time of 8ms (solid line). For similaralkynylplatinum(II) in the presence of oxygen in THF solutions thephosphorescence decay time was found to be approximately200ns.[15] When oxygen was evacuated a dramatic increase of thephosphorescence decay time was observed, reaching up to a fewhundred ms. The latter corresponds well with theoreticalestimations of the radiative decay time from density functionaltheory calculations.[28] The decay time measured for our solid(8ms) is intermediate between the oxygen-quenched and oxygen-evacuated situation in the solutions. Interestingly, the relativecontribution of phosphorescence to fluorescence can be under-stood from the phosphorescence decay time. In oxygen-saturatedsolvent the fluorescence yield dominates over the phosphores-cence. In oxygen-evacuated solvents the phosphorescence yieldtotally dominates the luminescence spectrum. In the solids with

& Co. KGaA, Weinheim Adv. Funct. Mater. 2009, 19, 235–241

FULLPAPER

www.afm-journal.de

Figure 8. a) Emission and excitation spectra and b) time-resolved phosphorescence decay of hybrid glass 1b. The emission was recorded for excitation at

356 nm. The excitation spectrum was obtained by monitoring the emission at 520 nm while scanning the excitation monochromator. The time resolved

decay was recorded with 356 nm excitation and 520 nm emission. The solid line is a fitting with decay time of 8 microseconds.

intermediate phosphorescence decay time, both appear atcomparable magnitude.

OPL properties of 90 and 120mM hybrid glasses weremeasured in an f/5 arrangement, at wavelengths of 480 nm,532 nm, 580 nm and 630 nm, using an Nd:yttrium aluminiumgarnet (YAG)/optical parametric oscillator (OPO) laser delivering5 ns pulses for excitation. A representative OPL curve in terms ofthe transmitted pulse energy versus the input pulse energy in therange up to 150mJ is shown in Figure 9. For the laser pulse energyin the range of 100–200mJ, approximately constant clampingvalues of transmitted energies (Eout) were found. The results ofthe clamping values for the different wavelengths are summar-ized in Table 1. For the 120-mM hybrid solid, the Eout values were

Figure 9. OPL response at 532 nm (sample 1b–SiOx; 120mM)

Table 1. Optical power limiting measurements showing the highest trans-mitted energy observed for a ns-pulsed laser focused in the hybridmaterials versus the wavelength (input 170mJ).

Material 480 nm (mJ) 532 nm (mJ) 580 nm (mJ) 630 nm (mJ)

1b – SiOx (120mM) 0.2 3 4.5 7

1b–SiOx (90mM) 1 3.5 4.5 8


0.2, 3, 4.5 and 7mJ at 480, 532, 580 and 630 nm, respectively. It isinteresting to compare these results with previously reported dataof similar chromophores in solutions. Acetonide dendrimersbased on 1, as well as the uncapped Pt-ethynyl, were all shown tohave OPL clamping values in the range 6–8mJ at 532 nm for30mM samples in THF solutions, measured in the sameexperimental set-up.[13] Moreover, 50mM of triazole- and30mM of thiophenyl-functionalized analogues in THF werefound to give clamping values in the range 2–8mJ at 532 nm(at 170-mJ Ein).

[16,29] The analogue triazole-functionalizedPt-ethynyl dispersed in PMMA matrices has also recently beenreported on.[26] Here, the best OPL clamping value was approx.3mJ at 532 nm (at 100-mJ Ein).

Thus, using the new hybrid glass materials at 90–120mMnominal concentration we obtained better or similar values thanthose previously reported using THF solutions or PMMAmatrices. There are some advantages using the solid sol–gelmatrix compared to solutions and polymer glasses. Obviously, thesolid can be polished and further post-processed, but solventscannot. Using PMMA, similar results and solid materialproperties were obtained, however, the Tg of the doped PMMAmatrix was found to be in the range 100–113 8C [26], which limitsits use in harsh environments.

3. Conclusions

Platinum (II) acetylide molecules for optical power-limitingapplications were functionalized with alkoxysilane groups, andincorporated into a glass matrix prepared by a modified sol–gelmethod. The process was optimized and the influence of thehydrolysis parameters and catalyst were elucidated. The modifiedprocess allowed preparation of optically pure organic-inorganicmonolithic glass materials which showed broadband opticallimiting with low clamping values at visible wavelengths. Thesolid OPL materials allowed post-processing such as cutting andpolishing. From the optical power limiting measurements on thehybrid materials, it was found that the properties observed for thechromophore in the solid sol–gel matrix were comparable to


FULLPAPER

www.afm-journal.de

240

those in solution or PMMA matrices. This sol–gel approach withfine tuning of the nanostructure of the material finally appears tobe a facile and efficient route to produce solid-state support fororganoplatinum chromophores. Optical quality glasses withstrong non-linear absorption were obtained.

4. Experimental

General: The compounds 1,4-dimethoxybenzene, 5-bromo-2-thiophe-necarbaldehyde, trans-PtCl2(PBu3)2 (� 98%) and other chemicals werepurchased from Sigma-Aldrich Co and used without further purification.THF and TEA were distilled from potassium and potassium hydride,respectively. Compound 3a [13], and 1,4-diiodo-2,5-dimethoxy-benzene[30,31], were synthesized similar to previously described literatureprocedures. The reactions were carried out in Ar atmosphere. TLC wasperformed on Silica Gel 60 F254 (Merck). Flash column chromatography(eluent given in square brackets) was performed on silica gel (matrix, 60 A,35–70mm, Grace Amicon). 1H and 13C NMR spectra were recorded on aBruker DRX 400 or a Bruker DRX 360 at 298 K, and chemical shifts arereported relative to CHCl3 (dH 7.26 ppm) or CDCl3 (dC 77.0 ppm) solventsignals. IR spectra were recorded on an ATIMattsonGenesis Series FTIRTM

spectrometer. The refractive indices were measured using multi-wavelength m-lines spectroscopy (MWMLS) [32].

The optical-limiting spectra were recorded with a f/5 focusing systemusing a frequency doubled Nd:YAG laser equipped with a OPO delivering5 ns pulses. A single pulsemode was used to avoid damage during the OPLexperiments [33,34]. The transmission spectra were recorded using a CARY5G UV-vis-NIR spectrophotometer.

A Titanium:Sapphire laser (Coherent Mira 900-f) was used as radiationsource for emission experiments and time-resolved emission measure-ments. The fundamental output from the mode-locked laser gave pulses ofapproximately 200 femtosecond duration and 76MHz pulse repetitionfrequency (prf). The pulse repetition frequency was controlled by anacousto-optic modulator (Coherent 9200 Pulse Picker) between 9 kHz and4.75MHz. Single-photon excitation experiments were performed byfrequency doubling of the fundamental output to below 400 nm using asecond harmonic generation crystal (Inrad Ultrafast Harmonic GenerationSystem, Model 5-050. Steady state emission spectra were recorded byscanning the monochromator in front of the PMT. Excitation spectra weretaken using an IBH 5000 submicrosecond xenon flashlamp as light source.For more details, see ref. [17].

Compound 4a: Compound 3a (0.215 g, 0.926mmol) and trans-PtCl2(PBu3)2 (0.310 g, 0.463mmol) were mixed in TEA (4mL) and THF(4mL) and heated to 60 8C. When a clear solution appeared, CuI (9mg,0.05mmol) was added. After 6min the reaction was allowed to reach roomtemperature. The residue was diluted with CHCl3 and washed twice with1MHCl (aq). The organic extract was dried with anhydrousMgSO4, filteredand concentrated. Recrystallization from hexane/CHCl3 gave yellowcrystals (0.392 g, 0.369mmol) in 80% yield. 1H NMR (400MHz, CDCl3,d): 7.51 (d, J¼ 8.3Hz, 4 H), 7.38 (d, J¼ 8.3Hz, 4 H), 7.33 (d, J¼ 8.3Hz, 4H), 7.23 (d, J¼ 8.3Hz, 4 H), 4.69 (s, 4 H), 2.22–2.02 (m, 12 H), 1.69–1.53(m, 12 H), 1.53–1.37 (m, 12 H), 0.93 (t, J¼ 7.3Hz); 13C NMR (100MHz,CDCl3, d): 140.7, 131.6, 131.2, 130.6, 129.1, 126.8, 122.8, 119.1, 111.8(apparent t, J¼ 14.7Hz), 109.3, 90.1, 89.6, 64.9, 26.3, 24.4 (apparent t,J¼ 7Hz), 23.9 (apparent t, J¼ 17Hz), 13.8.

Compound 3b: 1,4-Diiodo-2,5-dimethoxy-benzene (3.00 g, 7,69mmol),CuI (15mg, 0.08mmol), PPh3 (10mg, 0.04mmol) and PdCl2(PPh3)2 (28mg,0.04mmol) were dissolved in a mixture of argon deairated TEA (10mL) andTHF (10mL). (4-Ethynylphenyl)methanol (1.02 g, 7.69mmol) dissolved inTHF (4mL) was added dropwise to the reaction mixture. After stirring at60 8C for 15min, ethynyltrimethylsilane (0.76 g, 7.7mmol) was added andthe reaction was allowed to run for an additional 20min. Subsequently, thesolution was allowed to reach room temperature and was diluted with CHCl3and washed with 1MHCl (aq). The organic phase was dried with anhydrousMgSO4, filtered and concentrated. The residue was dissolved in THF (40mL)and EtOH (20mL), and KOH (560mg, 9.98mmol) in water (2mL) was

� 2009 WILEY-VCH Verlag GmbH

added. After 10min stirring at room temperature the reaction wasconcentrated and dissolved in CHCl3. The organic mixture was washedwith 1M HCl (aq) and dried with anhydrous MgSO4, filtered, andconcentrated. Flash chromatography over silica (heptane:EtOAc 2:1)followed by recrystallization from CHCl3/MeOH gave a slightly yellow solid(0.50 g, 1.7mmol) in 22% yield. 1H NMR (400MHz, CDCl3, d): 7.56 (d,J¼ 8.0Hz, 2 H), 7.36 (d, J¼ 8.0Hz, 2 H), 7.02 (s 1 H), 7.0 (s, 1 H), 4.73 (d,J¼ 5.9Hz, 2 H), 3.89 (s, 3 H), 3.88 (s, 3 H), 3.41 (s, 1 H), 1.69 (t, J¼ 5.9Hz,1 H); 13CNMR (100MHz, CDCl3, d): 154.4, 153.7, 141.2, 131.8, 126.7, 122.2,116.1, 115.4, 114.0, 111.8, 95.0, 85.4, 82.6, 79.9, 64.9, 56.41, 56.36.

Compound 4b: Compound 3b (0.136 g, 0.466mmol) and trans-PtCl2(PBu3)2 (0.149 g, 0.222mmol) were mixed in TEA (2mL) and THF(2mL) and heated to 60 8C. When a clear solution appeared, a catalyticamount of CuI was added, and after 6min the reaction was allowed to reachroom temperature. The residue was diluted with CHCl3 and washed twotimes with 1M HCl (aq). The organic extract was dried with anhydrousMgSO4(s), filtered and concentrated. Flash chromatography over silica(heptane: EtOAc 1:1) gave a yellow solid (0.392 g, 0.369mmol) in 99%yield. 1H NMR (400MHz, CDCl3, d): 7.53 (d, J¼ 8.1Hz, 4 H), 7.30 (d,J¼ 8.1Hz, 4 H), 6.89 (s, 2 H), 6.82 (s, 2 H), 4.66 (s, 4H), 3.83 (s, 6 H), 3.78(s, 6 H), 2.29–2.13 (m, 12 H), 2.08 (broad s, 2 H), 1.67–1.54 (m, 12 H),1.51–1.38 (m, 12 H), 0.91 (t, J¼ 7.2Hz, 18 H); 13C NMR (100MHz, CDCl3,d): 153.83, 153.80, 140.7, 131.6, 126.6, 122.8, 119.7, 116.4 (apparent t,J¼ 14.7Hz), 115.4, 115.1, 108.8, 105.1, 93.4, 86.5, 64.8, 56.2, 55.9, 26.3,24.3 (apparent t, J¼ 7Hz), 23.5 (apparent t, J¼ 17Hz), 13.8.

Compound 1b: Compound 4a (100mg, 0.094mmol) was dissolved inTHF (2.0ml) under argon atmosphere. ICTES (93mg, 0.38mmol) and twodrops of TEA were added to the solution. The reaction was heated in asealed flask overnight at 105 8C in an oil bath. After the reactionmixture hadreached room temperature, THF was removed by evaporation. The residuewas triturated five times with hexane and dried under vacuum which gave aslightly yellow solid (63mg, 0.040mmol) in 43% yield. 1H NMR (400MHz,CDCl3, d): 7.49 (d, J¼ 8.1Hz, 4 H), 7.37 (d, J¼ 8.1Hz, 4 H), 7.31 (d,J¼ 8.1Hz, 4 H), 7.22 (d, J¼ 8.1Hz, 4 H), 5.09 (s, 4 H), 5.04 (t, J¼ 5.5Hz, 2H), 3.81 (q, J¼ 7.0Hz, 12 H), 3.24–3.16 (m, 4 H), 2.18–2.06 (m, 12 H),1.70–1.55 (m, 16H), 1.50–1.39 (m, 12H), 1.26 (t, J¼ 7.0Hz, 18 H), 0.92 (t,J¼ 7.3Hz, 18 H), 0.66–0.59 (m, 4 H); 13C NMR (100MHz, CDCl3, d):156.2, 136.6, 131.5, 131.2, 130.6, 127.9, 123.2, 119.1, 111.8 (apparent t,J¼ 15Hz), 109.3, 90.3, 89.5, 66.0, 58.4, 43.3, 26.3, 24.4 (apparent t,J¼ 7Hz), 23.9 (apparent t, J¼ 17Hz), 23.2, 18.2, 13.8, 7.6.

Compound 2b: Compound 4b (158mg, 0.136mmol) was dissolved inTHF (3mL) under argon atmosphere. ICTES (132mg, 0.535mmol) andthree drops of TEA were added to the solution. The reaction was heated in asealed flask for 36 h at 104 8C in an oil bath. After the reaction mixture hadreached room temperature, THF was removed by evaporation. The residuewas triturated five times with hexane and dried under vacuum, which gave ayellow solid (198mg, 0.180mmol) in 88% yield. 1H NMR (400MHz,CDCl3, d): 7.51 (d, J¼ 8.1Hz, 4 H), 7.30 (d, J¼ 8.1Hz, 4 H), 6.90 (s, 2 H),6.81 (s, 2 H), 5.14–5.02 (m, 6 H), 3.92–3.70 (m, 24 H), 3.23–3.11 (m, 4H),2.28–2.08 (m, 12 H), 1.71–1.50 (m, 16 H), 1.50–1.35 (m, 12 H), 1.21 (t,J¼ 7.0Hz, 18 H), 0.90 (t, J¼ 7.3Hz, 18 H); 13C NMR (100MHz, CDCl3, d):156.2, 153.9, 153.8, 136.4, 131.5, 127.7, 123.4, 119.8, 116.5 (apparent t,J¼ 15Hz), 115.4, 115.1, 108.7, 105.0, 93.2, 86.9, 66.0, 58.4, 56.2, 55.9,43.4, 26.3, 24.3 (apparent t, J¼ 7Hz), 23.5 (apparent t, J¼ 17Hz), 23.2,18.2, 13.8, 7.6.

Preparation of Materials; Typical Procedure for the Preparation of GraftedHybrids: In procedure (c), the materials were prepared by using MTEOS asstarting precursor hydrolyzed in acidic medium (H2O, HCl or AcOH,pH¼ 2.5) in the presence of ethanol (molar ratio EtOH/MTEOS¼ 3). Thehydrolysis molar ratio water/precursor was 3. The mixture was stirredovernight and evaporated to the initial volume of precursor. APTES solutionin ethanol was added to neutralize the sol. In the second step, the dyes wereadded to the sol as a solution in THF with the desired concentration.Addition of H2O (pH 2.6) and stirring of the mixture during 7 days wasnecessary to achieve hydrolysis and condensation of the chromophore withthe matrix and prevent precipitation of the dye during the drying step. Afteraging was finished, the gels were dried between 70 and 110 8C in PTFEmoulds. The volume after shrinkage was approximately half of the original

& Co. KGaA, Weinheim Adv. Funct. Mater. 2009, 19, 235–241

FULLP

www.afm-journal.de

volume. In procedure (a), a similar sol was used but the chromophore wasadded prior to neutralization with APTES. Regarding procedure (b), the solwas the same as for (a) and (c), but the chromophore was slightlyhydrolyzed separately prior to addition to the sol and neutralization.

APER
Acknowledgements
Support to BE, CL, ML and SP from the ‘Swedish Defence NanotechnologyProgram’ is gratefully acknowledged. We thank Lars-Goran Heimdal fortechnical assistance.

Received: July 17, 2008

Published online: December 12, 2008

[1] R. C. Hollins, Curr. Opi. Solid State Mat. Sci. 1999, 4, 189.

[2] C. W. Spangler, J. Mater. Chem. 1999, 9, 2013.

[3] C. F. Li, L. Zhang, M. Yang, H. Wang, Y. X. Wang, Phys. Rev. A 1994, 49,

1149.

[4] J. W. Perry, K. Mansour, I. Y. S. Lee, X. L. Wu, P. V. Bedworth, C. T. Chen, D.

Ng, S. R. Marder, P. Miles, T. Wada, M. Tian, H. Sasabe, Science 1996, 273,

1533.

[5] T. J. McKay, J. A. Bolger, J. Staromlynska, J. R. Davy, J. Chem. Phys. 1998, 108,

5537.

[6] J. E. Ehrlich, X. L. Wu, I. Y. S. Lee, Z. Y. Hu, H. Rockel, S. R. Marder, J. W.

Perry, Opt. Lett. 1997, 22, 1843.

[7] G. S. He, J. D. Bhawalkar, C. F. Zhao, P. N. Prasad, Appl. Phys. Lett. 1995, 67,

2433.

[8] G. S. He, R. Gvishi, P. N. Prasad, B. A. Reinhardt,Opt. Commun. 1995, 117,

133.

[9] B. A. Reinhardt, L. L. Brott, S. J. Clarson, A. G. Dillard, J. C. Bhatt, R. Kannan,

L. X. Yuan, G. S. He, P. N. Prasad, Chem. Mater. 1998, 10, 1863.

[10] J. Staromlynska, T. J. McKay, J. A. Bolger, J. R. Davy, J. Opt. Soc. Am. B 1998,

15, 1731.

[11] T. M. Cooper, D. G. McLean, J. E. Rogers, Chem. Phys. Lett. 2001, 349, 31.

[12] J. E. Rogers, T. M. Cooper, P. A. Fleitz, D. J. Glass, D. G. McLean, J. Phys.

Chem. A 2002, 106, 10108.

[13] R. Vestberg, R. Westlund, A. Eriksson, C. Lopes, M. Carlsson, B. Eliasson,

E. Glimsdal, M. Lindgren, E. Malmstrom, Macromolecules 2006, 39, 2238.


[14] C. Desroches, C. Lopes, V. Kessler, S. Parola, Dalton Trans. 2003, 2085.

[15] M. Lindgren, B. Minaev, E. Glimsdal, R. Vestberg, R. Westlund, E. Mal-

mstrom, J. Lumin. 2007, 124, 302.

[16] P. Lind, D. Bostrom, M. Carlsson, A. Eriksson, E. Glimsdal, M. Lindgren, B.

Eliasson, J. Phys. Chem. A 2007, 111, 1598.

[17] E. Glimsdal, M. Carlsson, B. Eliasson, B. Minaev, M. Lindgren, J. Phys.

Chem. A 2007, 111, 244.

[18] G.-J. Zhou, W.-Y. Wong, C. Ye, Z. Lin, Adv. Funct. Mater. 2007, 17, 963.

[19] G.-J. Zhou, W.-Y. Wong, Z. Lin, C. Ye, Angew. Chem, Int. Ed. 2006, 45, 6189.

[20] G.-J. Zhou, W.-Y. Wong, D. Cui, C. Ye, Chem. Mater. 2005, 17, 5209.

[21] C. Sanchez, B. Lebeau, F. Chaput, J.-P. Boilot, Adv. Mater. 2003, 15, 1969.

[22] a) G. Brusatin, P. Innocenzi, M. Guglielmi, R. Signorini, R. Bozio,Nonlinear

Opt. 2001, 27, 259; b) P. Innocenzi, G. Brusatin, Chem. Mater. 2001, 13,

3126; c) N. Sanz, A. Ibanez, Y. Morel, P. L. Baldeck, Appl. Phys. Lett. 2001,

78, 17 2569; d) C. Desroches, S. Parola, D. Cornu, P. Miele, P. L. Baldeck, C.

Lopes, Mat. Res. Soc. Symp. Proc. 2003, 771, 237; e) M. Ortenblad, S.

Parola, F. Chaput, C. Desroches, C. Sigala, J. M. Letoffe, P. Miele, P. L.

Baldeck, B. Eliasson, A. Eriksson, C. Lopes,Mat. Res. Soc. Symp. Proc. 2005,

847, 405; f) S. Parola, R. Zieba, C. Desroches, F. Chaput, E. Malmstrom, M.

Lindgren, B. Eliasson, C. Lopes, Proc. SPIE 2006, 6401.

[23] N. K. Raman, M. T. Anderson, C. J. Brinker, Chem. Mater. 1996, 8,

1682.

[24] D. Riehl, F. Chaput, Y. Levy, J.-P. Boilot, F. Kajzar, P. A. Chollet, Chem. Phys.

Lett. 1995, 245, 36.

[25] P. Judeinstein, C. Sanchez, J. Mater. Chem. 1996, 6, 511.

[26] R. Westlund, E. Malmstrom, C. Lopes, J. Ohgren, T. Rodgers, Y. Saito, S.

Kawata, E. Glimsdal, M. Lindgren, Adv. Funct. Mater. 2008, 18, 1939.

[27] T. J. McKay, J. Staromlynska, P. Wilson, J. Davy, J. Appl. Phys. 1999, 85, 1337.

[28] B. Minaev, E. Jansson, M. Lindgren, J. Chem. Phys. 2006, 9, 094306/1–

094306/11.

[29] R. Westlund, E. Glimsdal, M. Lindgren, R. Vestberg, C. Hawker, C. Lopes, E.

Malmstrom, J. Mater. Chem. 2008, 18, 166.

[30] T. Sargent, III, A. T. Shulgin, C. A. Mathis, J. Med. Chem. 1984, 27,

1071.

[31] A. M. Ramos, M. T. Rispens, J. K. J. van Duren, J. C. Hummelen, R. A. J.

Janssen, J. Am. Chem. Soc. 2001, 123, 6714.

[32] R. Ulrich, R. Torge, Appl. Opt. 1973, 12, 2901.

[33] D. Vincent, MCLC S&T, Sect. B: Nonlinear Opt. 1999, 21, 413.

[34] D. Vincent, J. Cruickshank, Appl. Opt. 1997, 36, 7794.


Preparation of Functional Hybrid Glass Material from Platinum (II) Complexes for Broadband Nonlinear...

Documents

Transcript of Preparation of Functional Hybrid Glass Material from Platinum (II) Complexes for Broadband Nonlinear...