24 CMDITR Review <strong>of</strong> Undergraduate Research Vol. 2 No. 1 Summer <strong>2005</strong>
Synthesis <strong>of</strong> Nonlinear Optical-Active MaterialsDan Daranciang, <strong>Washington</strong> <strong>University</strong> in St. LouisDonald Responte and Werner KaminskySynthesisDepartment<strong>of</strong><strong>of</strong>NonlinearChemistry, <strong>University</strong>Optical-Active<strong>of</strong> <strong>Washington</strong>MaterialsroductionSince the first observation Dan Daranciang <strong>of</strong> second harmonic<strong>Washington</strong> <strong>University</strong> in St. Louiseration (SHG) in 1961 by Franken, multiplelinear optical materialse been characterized anddied. Franken irradiated INTRODUCTIONrtz with 694 nm light, andhis surprise, he detecteditted photons at 347 nm,f the original wavelengthThe key characteristic <strong>of</strong> all NLO active materialsis seen Donald in their Responte packed and lattice Werner geometry. Kaminsky In order toDepartment <strong>of</strong> Chemistryexhibit second-, <strong>University</strong> third-, or <strong>of</strong> nth-order <strong>Washington</strong>optical effects, theunit cell <strong>of</strong> the material must be noncentrosymmetric.Otherwise, upon excitation <strong>of</strong> thematerial, dipole-dipole METHODS vibrations occur in equalmagnitude but opposite direction, and therefore canceleach other out. Another consideration in our designwas how to ensure that our products, in addition tobeing NLO active, could potentially have photonicsapplications. We decided to use aromatic functionalgroups in our products. Aromatic rings containregions <strong>of</strong> high -electron density, which would giveSince the first observation <strong>of</strong> second harmonic generation The key characteristic <strong>of</strong> all NLO active materials is seen(SHG) in 1961 by Franken, multiple nonlinear optical materials in their packed lattice geometry. In order to exhibit second-,have been characterized and studied. Franken irradiated quartz third-, or nth-order optical effects, the unit cell <strong>of</strong> the materialwith 694 nm light, and to his surprise, he detected emitted photonsmust be non-centrosymmetric. Otherwise, upon excitation <strong>of</strong> theat 347 nm, half the original wavelength and therefore twice material, dipole-dipole vibrations occur in equal magnitude buttherefore twice thethe energy <strong>of</strong> the incoming photons.FigureThis1.singularSchematicobservation,<strong>of</strong>the opposite direction, and therefore cancel each other out. Anotherresult <strong>of</strong> a second order phenomenon SHG. Two involving photons the absorption <strong>of</strong> <strong>of</strong> consideration in our design was how to ensure that our products,two photons, spawned a new wavelength classification <strong>of</strong> materials: (red) are nonlinearin addition to being NLO active, could potentially have photon-optical (NLO) materials. NLO absorbed materials to promise reach a to have great our ics applications. compounds We the decided ability to use to aromatic readily functional transfer groups charge. inutility in developing Synthesis tomorrow’s <strong>of</strong> Nonlinear "virtual" technology. excited Optical-Active Taken state. together, A the Materials our products. Aromatic rings contain regions <strong>of</strong> high π-electronDan Daranciang, <strong>Washington</strong> <strong>University</strong> in St. Louissheer quantity and variety <strong>of</strong> Donald NLO single effects Responte photon that and have Werner at been Kaminsky /2 observed density, which would give our compounds the ability to readilyallow us to harness the properties Department <strong>of</strong> Chemistry, light in exciting <strong>University</strong> and <strong>of</strong> unexpectedways. Photonics-based technology sees use today in everything With this in mind, we chose to study the reaction <strong>of</strong> aryl iso-<strong>Washington</strong>(blue) emittedtransfer charge.IntroductionThe key characteristic <strong>of</strong> all NLO active materialsSince from the pulse first measurement observation <strong>of</strong> devices second to harmonic fiber optics. is seen in their packed lattice thiocyanates geometry. with In order (S)-2-butanol. to (S)-2-butanol is a relatively lowgeneration (SHG) in 1961 by Franken, multiple exhibit second-, third-, or nth-order molecular optical weight effects, chiral theNLO materials promise to have greatligand with only one possible nucleophilicnonlinear optical materialsunit cell <strong>of</strong> the material must be noncentrosymmetric.Otherwise, reaction, upon excitation and therefore <strong>of</strong> the its product with a substituted aryl isothio-have been characterized andstudied. Franken irradiatedmaterial, dipole-dipole vibrations cyanate is occur easily in predictable. equal Since it is chiral, the product wouldquartz with 694 nm light, andmagnitude but opposite direction, and therefore cancelhave a chiral carbon center, and we were therefore assured that theto his surprise, he detectedeach other out. Another consideration in our designemitted photons at 347 nm,was how to ensure that our unit products, cell <strong>of</strong> the in addition product to could not have a center <strong>of</strong> symmetry.half the original wavelengthbeing NLO active, could could potentially not have photonics a center <strong>of</strong> symmetry.and therefore twice theapplications. We decided to use aromatic functionalSenergy Figure <strong>of</strong> 1. the Schematic incoming <strong>of</strong> SHG.Figure 1. Schematic <strong>of</strong>SHG. Two Two photons photons <strong>of</strong> wavelength <strong>of</strong> λ groups (red) are in absorbed our products. Aromatic rings contain Nphotons. to reach This a "virtual" singular excited wavelength state. A single (red) photon are at λ/2 (blue) regions is emitted. <strong>of</strong> high -electron density, which would give COHobservation, the result <strong>of</strong> a absorbed to reach a our compounds the ability to readily transfer charge. +involving the absorption <strong>of</strong> single photon at /2S<strong>of</strong> aryl isothiocyanates with R (S)-2-butanol. (S)-2-(blue) is emittedtwo photons, amples spawned are KTiO a new 4and KDP, potassium dihydrogen butanol phosphate), is a relatively low molecular weight chiralsecond order phenomenonWhile many such"virtual" excited state. Amaterials have beenWith this in mind, we chose to study the reactiondiscovered (two ex-classification <strong>of</strong> materials: nonlinear optical (NLO) ligand with only one possiblea great deal <strong>of</strong> work remains. For one, though the “classic” examplesin developing <strong>of</strong> NLO tomorrow’s materials technology. have certainly Taken been proven isothiocyanate SHG active, is easily predictable. Since it is chiral,substituted nucleophilic phenyl reaction, isothiocyanate (S)-2-butanolmaterials. NLO materials promise to have great and therefore its product with a substituted arylutilitytogether, experimentation the sheer quantity we and have variety performed <strong>of</strong> NLO effects shows that other product compounds would have a chiral carbon center, and wethat have been observed allow us to harness the were therefore assured that the unit cell <strong>of</strong> the productproperties can have <strong>of</strong> light even in larger exciting SHG and efficiencies. unexpected ways. In addition, the current example<strong>of</strong> chromophores technology sees has use recently today attracted in much experimental N SHcould not have a center <strong>of</strong> symmetry.N SPhotonics-basedCOHeverything from pulse measurement devices to fiber+interest, but these compounds are difficult to synthesize, involveoptics.SROWhile lengthy many reaction such materials sequences, have been and discovered afford increasingly smaller percentexamples yields are at each KTiOstep.4 and KDP, potassiumSRsubstituted phenyl isothiocyanate (S)-2-butanol(twodihydrogen phosphate), a great deal <strong>of</strong> work remains.For one, We though proposed the “classic” this summer examples to <strong>of</strong> synthesize NLO and characterizeHN Smaterials by X-ray have certainly diffraction been and proven SHG SHG emission active, experiments a certainphenyl-substituted i-butyl-N-phenyl thiocarbamateexperimentation we have performed shows that otherclass <strong>of</strong> materials, i-butyl-N-phenyl thiocarbamates. Through thisOcompounds can have even larger SHG efficiencies. InRSaddition, work, the we current hypothesized example <strong>of</strong> that chromophores we could lay has out a basis for the simple,Figure 2. The reaction <strong>of</strong> aryl isothiocyanates with (S)-2-butanol. When Rattracted rational much synthesis experimental and design interest, <strong>of</strong> NLO but active materials, which = EWG, the isothiocyanate undergoes electrophilic attack at the cumulenerecentlyphenyl-substituted i-butyl-N-phenyl thiocarbamatethese compounds are difficult to synthesize, involvecarbon, affording the phenyl-substituted i-butyl-N-phenyl thiocarbamate.lengthy demonstrated reaction sequences, significant and afford activity increasingly compared to the compoundsThe geometry at the indicated carbon on the butanol is preserved.Figure 2. The reaction <strong>of</strong> aryl isothiocyanates with (S)-2-smaller currently percent yields in wide at each use. step.butanol. When R = EWG, the isothiocyanate undergoesWe proposed this summer to synthesize and electrophilic attack at the cumulene carbon, affording thecharacterize by X-ray diffraction and SHG emission phenyl-substituted i-butyl-N-phenyl CMDITR thiocarbamate. Review <strong>of</strong> Undergraduate The Research Vol. 2 No. 1 Summer <strong>2005</strong> 25experiments a certain class <strong>of</strong> materials, i-butyl-Nphenylthiocarbamates. Through this work, we preserved. preserved.geometry at the indicated carbon on the butanol ishypothesized that we could lay out a basis for the Aryl isothiocyanates were selected because <strong>of</strong> theirrgy <strong>of</strong> the incomingtons. This singularervation, the result <strong>of</strong> aond order phenomenonolving the absorption <strong>of</strong>photons, spawned a newssification <strong>of</strong> materials: nonlinear optical (NLO)terials.lity in developing tomorrow’s technology. Takenether, the sheer quantity and variety <strong>of</strong> NLO effectst have been observed allow us to harness theperties <strong>of</strong> light in exciting and unexpected ways.otonics-based technology sees use today inrything from pulse measurement devices to fiberics.hile many such materials have been discoveredo examples are KTiO 4 and KDP, potassiumydrogen phosphate), a great deal <strong>of</strong> work remains.r one, though the “classic” examples <strong>of</strong> NLOterials have certainly been proven SHG active,erimentation we have performed shows that otherpounds can have even larger SHG efficiencies. Inition, the current example <strong>of</strong> chromophores hasently attracted much experimental interest, butse compounds are difficult to synthesize, involvegthy reaction sequences, and afford increasinglyaller percent yields at each step.e proposed this summer to synthesize andracterize by X-ray diffraction and SHG emissioneriments a certain class <strong>of</strong> materials, i-butyl-Nnylthiocarbamates. Through this work, weWith this in mind, we chose to study the reaction<strong>of</strong> aryl isothiocyanates with (S)-2-butanol. (S)-2-butanol is a relatively low molecular weight chiralligand with only one possible nucleophilic reaction,and therefore its product with a substituted arylisothiocyanate is easily predictable. Since it is chiral,the product would have a chiral carbon center, and wewere therefore assured that the unit cell <strong>of</strong> the productFigure 2. The reaction <strong>of</strong> aryl isothiocyanates with (S)-2-butanol. When R = EWG, the isothiocyanate undergoeselectrophilic attack at the cumulene carbon, affording thephenyl-substituted i-butyl-N-phenyl thiocarbamate. Thegeometry at the indicated carbon on the butanol is
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TOWARD MOLECULAR RESOLUTION C-AFM W
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My name is Aaron Montgomery and I a
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1,1-DIPHENYL-2,3,4,5-TETRAKIS(9,9-D
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