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Outline of Discussion
Introduce liquid crystal science Explain the role of chirality in liquid crystals Discuss the ability of various dopants to induce chiral phases in liquid crystal hosts Delve into the significance and development of optically switchable dopants
Used in display devices
± LCD Televisions, digital watch displays, mood rings
Biological liquid crystals
± Phospholipids in the plasma membrane
Lyotropic liquid crystals
white liquid at 145.5 C ± transparent. clear liquid 178. in 1888 The substance seemed to have two distinct meliting points ± cloudy.Discovery! First observed by an Austrian chemist. Friedrich Reinitzer.5 C Molecular structure of Cholesteryl benzoate .
and dopant molecules Self-Assemble into unique supramolecular structures . solvent.Liquid Crystal Mesophase The liquid crystal state is between the solid and liquid phases ± Refered to as mesophase Display properties of both crystal and liquid Sensitive to temperature. electric and magnetic fields.
Liquid Crystal Mesophase .
Order Parameter S Mesogens align along a common axis called a director (n) Can align with directional or positional orientation ± Describes different liquid crystal phases Degree of order expressed by parameter S .
Temperature Effect on parameter S At temperature Tc substance loses all order Anisotropic liquid crystal becomes isotropic liquid Tc = Clearing Temperature .
Liquid Crystal Classification Calamitic Discotic .
Chiral Smectic or Smectic C 4.Liquid Crystal Phases 1. Smectic A 3. Chiral Nematic or Cholesteric . Nematic 2.
Nematic Phase (N) Molecules exhibit long range orientational order Mesogen aligns long axis with a common director n .
Smectic Phases In the smectic phases molecules flow freely within a layer and align with a director n In Smectic C* phase the molecules align at an angle to the normal z .
Chirality A molecule can only be considered chiral if it lacks an axis of improper rotation ± Lacks an Sn axis Rotation by 360°/n followed by a reflection perpendicular to the axis of rotation Structure is non-superimposable on its mirror image Chirality can be induced upon a completely achiral molecule ± Chirality transfer ± Supramolecular chirality .
Chiral Nematic Also known as cholesteric phase or twisted nematic Molecules in this phase are chiral Helical change in orientation of the director Director has helical twist perpendicular to the long axis of helix Helical propagation of the director is nonsuperimposable on its mirror image .
Chiral Nematic n Pitch (p) is the distance in which the director rotates 360° .
Doped Liquid Crystals Chiral dopant ± Chiral guest molecule is dissolved into a nematic host Magnitude of cholesteric pitch Sign of cholesteric pitch ± Right handed helix is positive (P) ± Left handed helix is negative (M) P (+) M (-) .
Helical Twisting Power The efficiency of a dopant to induce helical organization ± Helical twisting power ( ) The pitch is inversely proportional to: ± Concentration (c) ± Helical twisting power ( ) ± Enantiomeric excess (ee) .
Chirality Transfer Chirality is amplified and transferred throughout the whole system .
Advantages of Doped LCs Doped liquid crystals have advantages over liquid crystals with chiral mesogens ± Pitch of helix is tunable by changing host-guest ratio ± Colors can be generated by a single dopant ± Host and dopant self assemble .
Shape Persistent Dopants Mesogenic functionalism Chiral coordination complexes TADDOL and Dioxolane compounds Atropisomer-based dopants .
Mesogenic Functionalism (R)-octan-2-ol Chiral alcohol dopant A chiral molecule is functionalized to liquid crystal mesogen Functionalization enhances solubility and molecular interaction with LC host Chiral alcohol attached to mesogen .
Amine Functionalization with Anthraquinone Intramolecular hydrogen bonding locks dopant conformation amine molecule Amine molecule attached to anthraquinone .
Color test for enantiomeric excess High helical twisting power of 18 caused liquid crystal to reflect light in the visible range The color of the liquid crystal is dependent on the enantiomeric excess of the dopant .
Chiral Coordination Complexes as Dopants Chirality of a coordination compound can be from chiral ligand or chiral metal center ± Chiral metal center can be (Dextro) or (Levo) .
C2-symmetric ruthenium diketonate coordination complexes C2 axis .
Metal coordination improves helical twisting power Reduced conformation flexibility Chiral propeller shape of metal complex .
TADDOL and Dioxolane Dopants Tartaric acid derivative .
TADDOL and Dioxolane Dopants .
Methyl groups on 31 and silane bridge on 32 prevent intramolecular hydrogen bonding between the diols .
Helical twisting power is greater in guest-host combinations where aryl core distances are of similar length -stacking interactions between dopant and biphenyl LC core .
interactions Non-covalent intermolecular interaction Arise from a combination of van der Waals and electrostatic forces Forms supramolecular structure ..interactions are still actively debated .
Proposed Dopant-Mesogen Interaction .
Atropisomer Dopants Atropisomer considered chiral because rotation around bond is sterically restricted .
Atropisomer Dopants If substitution at the 2 and 2 positions are covalently or hydrogen bonded Cisoid conformation is preferred Substitution by large unlinked constituents Transoid conformation preferred .
Atropisomer Dopants .
Proposed model for chirality transfer between binaphthyl dopant and liquid crystal mesogen .
Bistable Switchable Dopants Allows control of supramolecular chirality by external stimuli Can change helical: ± Sign ± Pitch length (p) Photochemical switchable dopants .
Control of supramolecular chirality using external stimuli .
Bistable Switchable Dopants External Stimuli ± pH ± Pressure ± Electric field ± Heat ± Magnetic field ± Light .
Bistable Switchable Dopants Potential use as molecular switch ± Molecular equivalent of transistor Nanotechnology Light versus electricity ± Less heat produced ± Light more efficient and abundant ± Faster data processing .
Optical Switches Type 1 ± Dopant switches enantiomeric state by irradiation with circularly polarized light ± Switch between P and M helicities .
Optical Switches Type 2 ± Dopant switches between diastereomers ± Chirality of dopant is inversed ± Dopant states are not enantiomers .
Optical Switches Type 3 ± Switch and chiral auxiliary are separate units ± Chirality change is not as strong .
4% Not strong enough to induce helical change due to low helical twisting power .Type 1 dopants: bicyclic ketones Circularly polarized light induces deracemization with enantiomeric excess of 0.
Type 1 dopants: bicyclic ketones .
Type 1 dopants: bicyclic ketones
ZLI-1167 Liquid Crystal Host
Mesogen resembling group incorporated that matches LC ZLI1167 aided in solubility and helical twisting power 13 mol% racemic 83
Type 2 dopants: overcrowded alkenes
2-(2,6-dimethylphenyl)-9-(2 ,3 -dihydro-1 H-naphtho[2,1-b]thiopyran-1 -ylidene)-9H-thioxanthene
Type 2 dopants: flourene derived molecular motor
Rotar Axle Stator Induces change in helical twist sign P-M
High helical twisting power possibly due to structural similarity of dopant and biphenyl core of host mesogen Thermal isomerisation from unstable to stable form is possible at room temperature = allows for reversible color change
Psuedoequatorial position with high steric strain .
Flourene Molecular Motor MBBA could not be used as mesogen because it absorbs <400 nm light The cycle was repeated 10 times with no reduction of being observed The textures always rotates clockwise during irradiation and anticlockwise during the thermal isomerization step .
Polygonal Surface Structure polyimide-coated glass surface Surface topography of polygonal nematic surface .
E7 with 1 wt % of 1a dopant Irradiated with 365 nm light Each square is 15 second interval Clockwise rotation Transition from 1a 1b White bar is 50 m .
½P 1b 1c Thermal isomeration at 20 °C Reaction half-life of 9.9 min in toluene rotation .
p.m.Work created by molecular motor was used to move 5 X 28 m glass rod Photo chemical step 0. 1a 1b .67 r.
Thermal step 0.m.22 r. 1b 1c .p.
X8 speed .
Type 3 dopants: azobenzenes Azobenzenes can perform cis-trans reversible isomerization when irradiated with UV-Visible light ± Trans form is rod like Stabilizes liquid crystal ± Cis form is bent Destabilizes liquid crystal .
Type 3 dopants: azobenzene derived molecular motor High helical twisting power allows for color switching UV light causes 73 to change helicity .
faster data processing.Conclusion Liquid crystals are self assembling molecules ± Have both crystalline and liquid properties Chiral dopants can be added to change from the nematic to the cholesteric phase Dopants vary in their ability to induce cholesteric change described by the helical twisting power ( ) Current research is focused on developing optically switchable dopants with high helical twisting powers ± Switchable LCs could be used for nanotechnology. or molecular motors .
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March 09. et al. 14397-14407 Rienk Eelkema and. Feringa. Macroscopic Expression of the Chirality of Amino Alcohols by a Double Amplification Mechanism in Liquid Crystalline Media. Javier Vicario. Ben L. Michael M. Ben L. Rotational Reorganization of Doped Cholesteric Liquid Crystalline Films Journal of the American Chemical Society 2006 128 (44). Pollard M. Pollard.440(7081):163-163. Nathalie Katsonis.. Rienk Eelkema. Alessandro Bosco. Jongejan. Ben L. 13480-13481 Eelkema R. Nathalie Katsonis. Feringa and Rienk Eelkema at the University of Groningen. Journal of the American Chemical Society 2005 127 (39). Mahthild G. Broer. Photoinduced Reorganization of Motor-Doped Chiral Liquid Crystals: Bridging Molecular Isomerization and Texture Rotation Journal of the American Chemical Society 2008 130 (44). 2006. and. M. Molecular machines: Nanomotor rotates microscale objects Nature [serial online]. 14615-14624 . Netherlands Rienk Eelkema. Emmanuelle Lacaze.References Special thanks to research by Ben L. Alberta Ferrarini. Dirk J. Feringa. Feringa. Vicario J.