Student Project Abstracts 2005 - Pluto - University of Washington

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SYNTHESIS OF A POLYENE EO CHROMOPHORE: USING A DIELS-ALDER REACTION TO FORM A SIDE-CHAIN STRUCTUREScheme 2. Synthesis of polyene chromophore.temperature required to reverse and an activation energy similarto the poling temperature is ideal so that complete linking of thechromophores to the polymer occurs once they have already beenmostly aligned with the field. A DA reaction also exhibits essentialcharacteristics when taking processability into account becausethe chromophore can be bound to the polymer cleanly and in a controlledmanner without the need for solvents, catalysts or any otherexternal chemical processes—this is particularly important for moreefficient chromophores that are sensitive to their surroundings.This concept has been shown to work with nonlinear chromophoresalready, but difficulty arises when it is applied to highly efficientnonlinear chromophores. More efficient chromophores, bynature, are highly polar and consequently they are quite sensitiveto their chemical environment. This makes it exceedingly difficultto functionalize them without decomposing them completely.With this in mind, the objective was to synthesize severalpolyene-type chromophores with a dienophile group at R 1so thatit may combine with a diene-functionalized host-polymer to forma side-chain system via a DA reaction (figure 1). Other structuresare present at R 2and R 3to benefit from the advantages of furtherlimiting the chromophore-chromophore interactions. Once synthesized,the materials properties were analyzed.R 1=dienophile groupR 2=phenyl groupFigure 1. A polyene-type chromophore.EXPERIMENTALSynthesis of the polyene chromophore was carried out with afairly standard procedure (scheme 2).The maleimide functional group to be used as the dienophilewas synthesized as an acid chloride (scheme 3). Literature indicatedthat this reaction would only last a matter of hours howeverit was found to take significantly longer. [4] The first batch wasonly reacted for 3 hours and had a great deal of impurity, whichgreatly affected the functionalization results.Scheme 3. Production of acid chloride.The finished chromophore 8 was deprotected and the acidchloride 10 was added (scheme 4). The yield of this reaction wasnegligible due to the poor purity of the acid chloride. Despiteextremely low yield, chromatography indicated that the reactiondid occur as hoped for. To confirm the success of this reactionscheme, a sample of the AJC-139 chromophore was reacted for24 hours with purer acid chloride (scheme 5).This reaction was a success with 57% yield. A chromophoresimilar to the original was synthesized from an intermediate 16and a slightly different acceptor group (scheme 6).96 CMDITR Review of Undergraduate Research Vol. 2 No. 1 Summer 2005
NOTHERNFigure 2. Polymer Host.Scheme 4. Functionalization of polyene chromophore.At this point synthesis was considered complete and chromophore17 was embedded in an anthracene functionalized polymethyl-methacrylate(PMMA) host polymer with a 25 wt.%loading density (figure 2). It was spin-cast to form a .75um filmon a glass substrate half coated with conducting indium-tin-oxide(ITO) (120nm) particularly designed to be optically transparentat telecommunications wavelengths (1.3um). Three sampleswere prepared by sputteringSynthesis of a Polyenea goldEOelectrodeChromophoreonto the top of theDenis Nothern, Jingdong Luo, Alex K.-Y. Jenpolymer At this film point such synthesis that was they considered were half complete over and the ITO and half overchromophore 17 was embedded in an anthracene functionalizedthe glass (figure 3). This allowed a voltage to be applied acrosspoly-methyl-methacrylate (PMMA) host polymer with a 25.88 .12wt.% loading density (figure 2). It was spin-cast to form athe electrode and the ITO layer and pole the O polymer. OCH 3 O OWhile the.75um film on a glass substrate half coated with conductingpoling indium-tin-oxide voltage (ITO) was (120nm) being particularly applied, designed current to be passing through theoptically transparent at telecommunications wavelengthspolymer (1.3um). Three was samples carefully were prepared monitored by sputtering for indications a gold of damage to theelectrode onto the top of the polymer film such that they were Fig. 2. Polymer Host.film. half over During the ITO heating, and half over the the current glass (figure was 3). recorded This overtime. Onceallowed a voltage to be applied across the electrode and the ITO layer and pole the polymer.poled, While the the poling r 33voltage value was was being measured applied, current via passing the through reflection the polymer technique was carefully[3] .monitored for indications of damage to the film. During heating, the current was recordedThe results can be seen in the following section.overtime. Once poled, the r 33 value was measured via the reflection technique [3] . The results canbe seen in the following section.Figure 3. Poling setup.Scheme 5. Functionalization of AJC-139 chromophoreRESULTSFig. 3. Poling setup.Figure 4. Current Vs. Time.Scheme 6. Functionalization of 2 nd polyene cromophore.Results:All the samples were exposed Figure to 3. the Poling poling voltage setup.and then heated at a rate of 5 C/sec starting at 50 C. Thecurrent through the polymer layer varies over time as thesample is heated (figure 4). This gives an indication of whenAll the samples were exposed to the poling voltage and thenthe T g is being approached as the current reaches a localheatedmaxima (orata minimarate ofin the5°C/seccase of polymerstartingbreakdownat 50°C.andThe current throughcurrent is able to jump directly from the gold to the ITO).the polymer With a 25 layer wt.% loading varies density, over poling time with as 100V/um the sample is heated (figureat 111 C the r 33 value was found to be as high as 44pm/V4). (Table This 1). This gives is nearly an double indication the value for of the when less efficient the T gis being approachedchromophores previously implemented in such a side-chainFig. 4. Current Vs. Time.as scheme. the current The high poling reaches temperature a local is an maxima indication that (or the a minima in the case ofside-chains formed and that the thermal stability of the systempolymer will be good. breakdown Additionally, the and very current low current is at able such high to jump temperatures directly (4.5 uA from at 160theC)indicates that there is little phase separation between the polymer and the chromophores, whichgoldis in agreementto the ITO).with expectations for a side-chain structure.With a 25 wt.% loading density, poling with 100V/um atSample Field (V/um) Temp ('C) Current (uA) r 33 (pm/V)111°C the #1 r 33value 100.00 was found 160 to be as high 4.5 as 44pm/V 42 (Table 1).This is nearly double the value for the less efficient chromophorespreviously implemented in such a side-chain scheme. The 6 high of 7poling temperature is an indication that the side-chains formedand that the thermal stability of the system will be good. Additionally,the very low current at such high temperatures (4.5 uAat 160°C) indicates that there is little phase separation betweenthe polymer and the chromophores, which is in agreement withexpectations for a side-chain structure.CMDITR Review of Undergraduate Research Vol. 2 No. 1 Summer 2005 97
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The material is based upon work sup
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TABLE OF CONTENTSSynthesis of Dendr
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6 CMDITR Review of Undergraduate Re
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SYNTHESIS OF DENDRIMER BUILDING BLO
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throughout the work period. Five su
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12 CMDITR Review of Undergraduate R
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BARIUM TITANATE DOPED SOL-GEL FOR E
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BARIUM TITANATE DOPED SOL-GEL FOR E
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SYNTHESIS OF NORBORNENE MONOMER OF
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using different reaction conditions
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Synthesis of Nonlinear Optical-Acti
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quality of the XRD structures wasca
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Behavioral Properties of Colloidal
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Transmission electron microscopy ha
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areorient themselves with the elect
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Fabry-Perot modulators with electro
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QUANTIZED HAMILTON DYNAMICS APPLIED
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Page 46 and 47: INVESTIGATING NEW CLADDING AND CORE
Page 48 and 49: Dr. Robert NorwoodChris DeRoseAmir
Page 50 and 51: SYNTHESIS OF TPD-BASED COMPOUNDS FO
Page 52 and 53: SYNTHESIS OF TPD-BASED COMPOUNDS FO
Page 54 and 55: OPTIMIZING HYBRID WAVEGUIDESpropaga
Page 56 and 57: At closer spaces the second undesir
Page 58 and 59: SYNTHESIS AND ANALYSIS OF THIOL-STA
Page 60 and 61: 60 CMDITR Review of Undergraduate R
Page 62 and 63: QUINOXALINE-CONTAINING POLYFLUORENE
Page 64 and 65: QUINOXALINE-CONTAINING POLYFLUORENE
Page 68 and 69: SYNTHESIS OF DENDRON-FUNCTIONALIZED
Page 72 and 73: BUILDING AN OPTICAL OXIMETER TO MEA
Page 78 and 79: TOWARD MOLECULAR RESOLUTION C-AFM W
Page 80 and 81: TOWARD MOLECULAR RESOLUTION C-AFM W
Page 82 and 83: SYNTHESIS AND CHARACTERIZATION OF E
Page 84 and 85: My name is Aaron Montgomery and I a
Page 86 and 87: 1,1-DIPHENYL-2,3,4,5-TETRAKIS(9,9-D
Page 88 and 89: 1,1-DIPHENYL-2,3,4,5-TETRAKIS(9,9-D
Page 90 and 91: EFFECTS OF SURFACE CHEMISTRY ON CAD
Page 92 and 93: EFFECTS OF SURFACE CHEMISTRY ON CAD
Page 98 and 99: SYNTHESIS OF A POLYENE EO CHROMOPHO
Page 102 and 103: 102 CMDITR Review of Undergraduate
Page 104 and 105: CHARACTERIZATION OF THE MOLECULAR P
Page 108 and 109: OPTIMIZATION OF SEMICONDUCTOR NANOP
Page 110 and 111: OPTIMIZATION OF SEMICONDUCTOR NANOP
Page 112 and 113: CHARACTERIZATION OF THE PHOTODECOMP
Page 116 and 117: ELECTROLUMINESCENT PROPERTIES OF OR
Page 120 and 121: DETERMINATION OF MOLECULAR ORIENTAT
Page 122 and 123: DETERMINATION OF MOLECULAR ORIENTAT
Page 124 and 125: HYDROGEL MATERIALS FOR TWO-PHOTON M
Page 126 and 127: HYDROGEL MATERIALS FOR TWO-PHOTON M
Page 128 and 129: THE DESIGN OF A FLUID DELIVERY SYST
Page 130: THE DESIGN OF A FLUID DELIVERY SYST
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Student Project Abstracts 2005 - Pluto - University of Washington

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