Chirality,twist and structures of micellar lyotropic cholesteric liquid crystals in comparison to the properties of chiralic thermotropic phases

Phase chirality in disk-like lyotropic cholesteric phases (Ch(D)) was investigated, which was induced by addition of center and axial chiral dopants to achiral lyotropic nematic host phases (N(D)). In a lyotropic nematic matrix of the disk-like N(D) phase in the ternary system hexadecyldimethylethyl ammonium bromide (C16Me2EABr)/water/n-decanol, a disk-like lyotropic cholesteric phase Ch(D) was induced by addition of the axial optically active compound R(-)-1,1'-binaphthalene-2,2'-diyl-hydrogen-phosphate (BDP). The helical twisting power (HTP) of the BDP is generally lower than the HTP value of inducing substances with center chirality as cholesterol, prednisolone and taurocholic acid. At constant composition of the N(D) phase, the helix lengths were determined in dependence on the BDP and steroid concentration by means of evaluation of the 'spaghetti-like' texture using polarizing microscopy. The reciprocal helix lengths are changing linearly with rising BDP concentration. The properties of the Ch(D) phase (textures, helix lengths, structural parameters of the micelles) induced by the chiral compounds and changed by the composition of host phases can give information to the mechanism of chirality transfer from the molecular level to that of the micellar aggregates and finally, to the liquid crystalline superstructure. Furthermore, the matrix influence of the N(D) phase on the helix formation was examined at constant BDP and steroid concentration. The structure in the Ch(D) phase was described in terms of micelle parameters. Finally, the inducing properties of a center chiral optically active compound such as cholesterol, prednisolone and taurocholic acid were compared with those of the axial chiral compound BDP. Last but not least, the situation of the theoretical and structural background for helix formation in liquid crystals, e.g. the explanation of chiralic transfer between micelles is analyzed and discussed. Two main conditions are necessary to build up the helix in the Ch(D) phase: the formation of H-bridges; and the existence of a specific chiralic interaction energy between neighboring micelles in the cholesteric superstructure.     

Sugar Amphiphiles as Revealing Dopants for Induced Chiral Nematic Lyotropic Liquid Crystals

The existence of phase chirality in lyotropic liquid crystals still raises questions. The mechanisms behind the transfer of chirality throughout the long-range orientational order are not yet obvious. Guest/host systems with chiral dopants in achiral host phases offer the capability of systematic investigations. We demonstrate that the large amount of accessible sugar amphiphiles exhibits remarkable structure/property relations. Their helical twisting power HTP increases strongly with the number of sugar units of a dopant molecule. The spatial range of the chirality information reaching from a chirally doped micelle to adjacent aggregates is essential for the development of phase chirality. The induced twist of the lyotropic nematic host phase is highly sensitive to small changes of the sugar type (e.g., galacto- to glucopyranose). Depending on the nature of the host phase, either the alpha- or the beta-linkage of the sugar to the hydrophobic moiety of the sugar dopant results in larger HTP values. We propose that our amphiphilic sugar derivatives act like antennae to transfer chirality information. Their effectiveness as chiral dopants is due to a hydrophobic anchoring within the micelles and an extension of their chiral moiety far into the intermicellar region. The chirality transfer works especially well if the hydrophilic and chiral sugar moieties are oriented toward a neighboring micelle in the direction of the helix axis. Copyright 2001 Academic Press.     

Helical twisting power and compatibility in twisted nematic phase of new chiral liquid crystalline dopants with various liquid crystalline matrices

ABSTRACT

Four chiral dopants exhibiting smectic LC phases themselves were prepared and their helical twisting power (HTP) and thermal phase behaviour in mixtures with four various LC hosts were studied. The influence of host liquid crystal on HTP was evaluated and generally higher values were found for hosts with high birefringence. Unexpectedly, high enhancement was found for an LC-chiral dopant pair, both having a similar aromatic core – biphenyl ring substituted with polar group. All studied chiral dopants exhibited limited compatibility with the LC hosts in twisted nematic phase at room temperature. For one of the studied mixtures, it was able to obtain single twisted nematic phase with selective light reflection band with maximum at wavelength about 1.0 µm. Carboxylic acid-type dopants exhibited total compatibility with the studied host in single twisted nematic phase at elevated temperatures, allowing preparation of mixtures with reflection band in the visible range. In case of the carboxylic acid dopants, blue phases for optimised compositions were observed. Intermolecular hydrogen bonding between carboxylic acid proton and pyridine nitrogen of chiral dopants was found. Doping the LC host with these dopants led to slight enhancement of HTP value and higher solubility in the LC host.     

Influence of a Change in Helical Twisting Power of Photoresponsive Chiral Dopants on Rotational Manipulation of Micro‐Objects on the Surface of Chiral Nematic Liquid Crystalline Films

Herein we report a group of five planar chiral molecules as photon‐mode chiral switches for the reversible control of the self‐assembled superstructures of doped chiral nematic liquid crystals. The chiral switches are composed of an asymmetrically substituted aromatic moiety and a photoisomerizing azobenzene unit connected in a cyclic manner through methylene spacers of varying lengths. All the molecules show conformational restriction in the rotation of the asymmetrically substituted aromatic moiety in both the E and Z states of the azobenzene units resulting in planar chirality with separable enantiomers. Our newly synthesized compounds in pure enantiomeric form show high helical twisting power (HTP) in addition to an improved change in HTP between the E and Z states. The molecule with a diphenylnaphthalene unit shows the highest ever known initial helical twisting power among chiral dopants with planar chirality. In addition to the reversible tuning of reflection colors, we employed the enantiomers of these five compounds in combination with four nematic liquid crystalline hosts to study their properties as molecular machines; the change in HTP of the chiral dopant upon photoisomerization induces rotation of the texture of the liquid crystal surfaces. Importantly, this study has revealed a linear dependence of the ratio of the difference between HTPs before and after irradiation against the absolute value of the initial HTP, not the absolute value of the change in helical twisting power between two states, on the angle of rotation of micro‐objects on chiral nematic liquid crystalline films. This study has also revealed that a change in irradiation intensity does not affect the maximum angle of rotation, but it does affect the speed of rotational reorganization of the cholesteric helix.     

Biaxial phase and coexistence of the two uniaxial nematic phases in the system sodium dodecyl sulphate–decanol–D2O

The system sodium dodecyl sulphate (SDS)/decanol (DeOH)/water presents, with temperature increase, an unusual phase transition between a stable biaxial phase and a coexistence region of the two uniaxial nematic phases (discotic N_D + cylindrical N_C). This has been detected previously by several methods for a sample with water/SDS molar ratio M_w = 36. Here, this system is investigated changing the ratio M_w to 32, where previously the coexistence region was reported after a discotic N_D phase, without the biaxial phase. We report now the existence of a biaxial N_B in the temperature range of ~2°C, defining for both values of M_w and the phase sequence as N_B – (N_D + N_C) – N_C. The change in temperature is followed by conoscopic and orthoscopic optical techniques and also analysed through the curve obtained by the technique of digital image processing of the textures, which reveals a continuous transition N_D – N_B – (N_D + N_C). While the biaxial phase is stable for at least 10 hours, in a reproducible way, the coexistence region evolves with time, and drops of the discotic phase grow immersed in a N_C matrix. Results are explained in terms of recent theories dealing with stabilisation of mixtures of cylinders and discs.     

Theory of a helicoidal cholesteric phase induced by an external field

We present a mean field theory to describe a helicoidal cholesteric phase for mixtures of a chiral nematic liquid crystal (LC) and a polymer chain as well as for pure chiral nematic LC molecules in the presence of a longitudinal external field parallel to the pitch axis of a cholesteric (Ch) phase. The free energy of the helicoidal Ch phase (Ch_H) is derived as a function of a usual orientational order parameter and an order parameter of the Ch_H phase. On increasing the strength of the external field, we find that the Ch phase changes to the nematic (N) phase through the Ch_H phase. Depending on the temperature and the strength of the external field, we find the second-order N–Ch_H and Ch_H–Ch phase transitions and the first-order paranematic (pN)–N, pN–Ch_H and pN–Ch phase transitions. We also predict phase diagrams in mixtures of a flexible polymer and a Ch LC molecule under the external field.     

An experimental and computational study of calamitic and bimesogenic liquid crystals incorporating an optically active [2,2]-paracyclophane

Two liquid-crystalline materials containing an optically active (R)-4-hydroxy-[2,2]-paracyclophane group were prepared, one in which the chiral group is a bulky terminal unit and one in which it forms part of a terphenyl-like mesogenic unit. Both materials exhibit monotropic chiral nematic phases. Partial phase diagrams were constructed for mixtures of both materials with 5CB, allowing us to extrapolate pitch lengths and helical twisting power values (HTP) for each material. The HTP value of the material with a ‘locked’ paracyclophane is 70% higher than that of a ‘free’ paracyclophane and this is rationalised as being due to the reduction in conformational freedom of the former material relative to the later.     

On the parity in helical twisting power of Ru(III) 1,3-diketonates of C2 symmetry in nematic liquid crystals

It is demonstrated that the sign of helical twisting power (HTP) of an enantiomeric Ru(III) complex of type [Ru(acac)(2)L] can be switched by choosing L from either L(per) or L(para), which is elongated either perpendicular or parallel to the C(2) symmetry axis, and four states become available in combination with DeltaLambda-chirality of the metal center. Complexes 1-n, in which 4,4'-dialkoxylated dibenzoylmethanate ligands are used as L(per), and 2 having L(para) = 3-(4'-decyloxyphenyl)pentane-2,4-dionate ligand were prepared for this purpose. They were optically resolved into the enantiomers by means of a clay column chromatography, and their performance as chiral dopants was evaluated in nematic liquid crystals including a room-temperature system, N-methoxybenzylidene-4-n-butylaniline (MBBA), which allowed facile measurements of the helical pitch lengths and CD spectra in the induced chiral nematic states. The induced CD signals have provided a clear evidence for the helical inversion between the two structure types, 1 and 2, of the same chirality. The twisting power of these six-coordinate metal complexes and their structure versus twist sense correlations are interpreted by the shape model. Intrinsically high HTP of Delta-[Ru(acac)(2)L(per)] has also allowed for observation of the pitch band due to the selective reflection in the visible wavelength range at the doping level of 2 mol % in MBBA.     

Helix reversals as bad neighbors to liquid crystal organizations in cholesteric states and thermally reversible gels of poly(ALKYL isocyanates)

While the temperature dependence of the lyotropic cholesteric pitch of the single helical sense poly ((R)-2,6-dimethylheptyl isocyanate) is in line with theory, comparable data on this state produced by chiral doping of the lyotropic nematic state of poly(n-hexyl isocyanate) could suggest an interplay between the supramolecular chirality of the liquid crystal and the dynamic equilibrium of the left and right hand helical blocks in this otherwise racemic polyisocyanate. The exclusion of helix reversals, as undersireable kinks in the liquid crystal organization, could play a role in this effect. Such helix reversal exclusions can also explain the peculiar chiral optical changes associated with the thermally reversible gelation of poly(n-hexyl isocyanate) copolymers in hydrocarbon solvents. These gels likely arise by entering the broad biphasic region of the Flory phase diagram leading to the formation of liquid crystal aggregates.     

Influence of glycerol on the formation of lyotropic mesophases —microscopic texture observations for determining preliminary phase diagrams of binary K-soap/glycerol systems

Analogously to aqueous K-soap/water systems already examined, the glycerol-containing systems KC _n /G (KC _n ;n=12, 14, 16, 18, 22; G=glycerol) are also able to build up hexagonal, lamellar, optically isotropic, gel-like and crystalline phases. These preliminary phases have been identified by texture observations of contact samples and singular concentrations with a polarizing microscope. The appertaining phase regions have been plotted in the binary phase diagrams.Correspondences and differences between these systems have been elucidared by drawing a comparison. Mosaic texture and oily streaks are typical of the lamellar phase. Spherulites are mainly found in the heterogeneous two-phase region lamellar/isotropic. The textures of the hexagonal phase are of fan-like morphology. The appearance of the gel phase texture resembles globular or curd-like structures.The influences exerted by the increasing chain lengths of the K-soaps (KC _n ,n=12–22) on the phase regions in the binary systems (KC _n /G) can be described as follows. The concentrations required for forming the hexagonal and the lamellar phase respectively are shifted toward lower K-soap concentrations. The concentration range in which the hexagonal phase is stable is diminished. The temperature range in which the hexagonal phase is stable becomes larger. The upper temperature limit of the lamellar phase region is lowered.Binary aqueous and glycerol-containing K-soap systems have the following common features: The hexagonal phase is built up at low soap concentrations. The lamellar phase is formed at high soap concentrations. The lamellar phase is formed at high soap concentrations. An optically isotropic region is inserved between the lamellar and the hexagonal phase in aqueous and glycerol-containing systems of the types KC₁₄, KC₁₆ and KC₁₈. The temperature of the transition hexagonalisotropic phase (HS) runs through a maximum value. On increasing the chain length the formation of the hexagonal phase is shifted in the direction of lower soap concentrations.Aqueous and glycerol-containing K-soap mixtures differ in the following essential points: The lyotropic mesophases (H, L, I) of aqueous systems are formed at considerably lower soap concentrations than the corresponding phases of glycerol-containing systems. The lamellar phases of aqueous systems reach the regions of very low soap concentrations. The lyotropic mesophases of aqueous systems are built up at temperatures lower than the corresponding ones of glycerol-containing mixtures. In aqueous systems the concentration range of the lamellar phase increases with increasing chain length, in contrast to glycerol-containing systems where it is diminished.     

Optically Biaxial,Re‐entrant and Frustrated Mesophases in Chiral,Non‐symmetric Liquid Crystal Dimers and Binary Mixtures

Sixteen optically active, non‐symmetric dimers, in which cyanobiphenyl and salicylaldimine mesogens are interlinked by a flexible spacer, were synthesized and characterized. While the terminal chiral tail, in the form of either (R)‐2‐octyloxy or (S)‐2‐octyloxy chain attached to salicylaldimine core, was held constant, the number of methylene units in the spacer was varied from 3 to 10 affording eight pairs of (R & S) enantiomers. They were probed for their thermal properties with the aid of orthoscopy, conoscopy, differential scanning calorimetry and X‐ray powder diffraction. In addition, the binary mixture study was carried out using chiral and achiral dimers with the intensions of stabilizing optically biaxial phase/s, re‐entrant phases and important phase sequences. Notably, one of the chiral dimers as well as some mixtures exhibited a biaxial smectic A (SmA_b) phase appearing between a uniaxial SmA and a re‐entrant uniaxial SmA phases. The mesophases such as chiral nematic (N*) and frustrated phases viz., blue phases (BPs) and twist grain boundary (TGB) phases, were also found to occur in most of the dimers and mixtures. X‐ray diffraction studies revealed that the dimers possessing oxybutoxy and oxypentoxy spacers show interdigitated (SmA_d) phase where smectic periodicity is over 1.4 times the molecular length; whereas in the intercalated SmA (SmA_c) phase formed by a dimer having oxydecoxy spacer the periodicity was found to be approximately half the molecular length. The handedness of the helical structure of the N* phases formed by two enantiomers was examined with the aid of CD measurements; as expected, these enantiomers showed optical activities of equal magnitudes but with opposite signs. Overall, it appears that the chiral dimers and mixtures presented herein may serve as model systems in design and developing novel materials exhibiting the apolar SmA_b phase possessing D_2h symmetry and nematic‐type biaxiality.     

Phase‐Transfer‐Catalyzed Asymmetric Synthesis of Axially Chiral Anilides

Catalytic asymmetric synthesis of axially chiral o‐iodoanilides and o‐tert‐butylanilides as useful chiral building blocks was achieved by means of binaphthyl‐modified chiral quaternary ammonium‐salt‐catalyzed N‐alkylations under phase‐transfer conditions. The synthetic utility of axially chiral products was demonstrated in various transformations. For example, axially chiral N‐allyl‐o‐iodoanilide was transformed to 3‐methylindoline by means of radical cyclization with high chirality transfer from axial chirality to C‐centered chirality. Furthermore, stereochemical information on axial chirality in o‐tert‐butylanilides could be used as a template to control the stereochemistry of subsequent transformations. The transition‐state structure of the present phase‐transfer reaction was discussed on the basis of the X‐ray crystal structure of ammonium anilide, which was prepared from binaphthyl‐modified chiral ammonium bromide and o‐iodoanilide. The chiral tetraalkylammonium bromide as a phase‐transfer catalyst recognized the steric difference between the ortho substituents on anilide to obtain high enantioselectivity. The size and structural effects of the ortho substituents on anilide were investigated, and a wide variety of axially chiral anilides that possess various functional groups could be synthesized with high enantioselectivities. This method is the only general way to access a variety of axially chiral anilides in a highly enantioselective fashion reported to date.     

The Chiral Twist-Bend Nematic Phase (N*TB)

The twist-bend nematic, N_TB, phase has been observed for chiral materials in which chirality is introduced through a branched 2-methylbutyl terminal tail. The chiral twist-bend nematic phase, N*_TB, is completely miscible with the N_TB phase of the standard achiral material, CB6OCB. The N*_TB phase exhibits optical textures with lower birefringence than those observed for the achiral N_TB phase, suggesting an additional mechanism of averaging molecular orientations. The N*−N*_TB transition temperatures for the chiral materials are higher than the N_TB−N transition temperatures seen for the corresponding racemic materials. This suggests the double degeneracy of helical twist sense in the phase is removed by the intrinsic molecular chirality. A square lattice pattern is observed in the N* phase over a temperature range of several degrees above the N*_TB–N phase transition, which may be attributed to a non-monotonic dependence of the bend elastic constant.     

One Stone for Three Birds‐Rhodium‐Catalyzed Highly Diastereoselective Intramolecular [4+2] Cycloaddition of Optically Active Allene‐1,3‐dienes

RhCl(PPh₃)₃‐catalyzed [4+2] intramolecular cycloaddition of optically active axially chiral allene‐dienes afforded cis‐fused [3.4.0]‐bicyclic products with three chiral centers in good yields with an excellent chemo‐ and diastereoselectivity. A pair of enantiomers of such products was generated highly selectively from both enantiomers of starting allene‐dienes, indicating that the axial chirality dictated the absolute configurations of the three in situ generated chiral centers with a very high efficiency of chirality transfer.     

Ferroelectricity of induced S*C phases with novel chiral dopants

Abstract

Induced S*_C phases can be obtained by dissolving chiral dopants in achiral S_C host phases. If the chiral guest molecules bear a transverse dipole, ferroelectricity will occur. The novel dopants under discussion are characterized by chiral centres and the transverse dipole situated not in the alkyl end groups of the mesogenic molecules, but directly in their rigid cores. As a rigid core, analogues of decalin were used. In those dopants, rotation around the molecular long axis is sterically restricted. According to the microscopic model of Zeks, this leads to enhanced values of the spontaneous polarization P _s. The magnitude as well as the sign of the spontaneous polarization P _s of the S*_C phases induced by the novel dopants in different host phases has been investigated. It has been found for the first time that for a given dopant, the polarization as well as the sign of P _s depends on the structure of the host phase. The results are discussed in terms of two microscopic models. They can be understood taking into account the situation that the potential of the restricted long axial rotation is determined by the hard core interactions of the molecules involved or that an orientation of the host dipoles by a guest/host interaction takes place.     

Polymerisation in lyotropic liquid-crystalline phases of dioctadecyldimethylammonium bromide

The polymerisation of styrene in lyotropic liquid-crystalline (LC) phases of dioctadecyldimethylammonium bromide (DODAB) in water is explored. Amphiphile concentrations between 20 and 50 wt % are employed. The study is set out as a model study for polymerisation reactions in nonstabilised, nonfunctional bilayer systems. X-ray characterisation was used to assess the phase behaviour of the lyotropic mesophases before, during and after polymerisation. The DODAB/water system forms the lamellar phase within the concentration range considered. Addition of styrene to the lamellar phase of DODAB at an equimolar ratio induces a phase shift to a bicontinuous cubic phase at elevated temperatures near the phase-transition temperature. Upon polymerisation within this cubic phase, the phase structure is maintained if the system is kept at constant temperature; however, if the polymer/amphiphile phase is cooled, the lamellar phase, being typical of the DODAB/water system, is restored. It is concluded that, as a result of phase separation between the polymer and the amphiphile phase, the polymerisation in lyotropic LC phases does not provide a stable copy of the templating amphiphile phase. This is in analogy to the observations for polymerisations in other lyotropic phases. Received: 16 March 2000 Accepted: 1 July 2000     

Cover Feature: Chirality Transfer from an Innately Chiral Nanocrystal Core to a Nematic Liquid Crystal 2: Lyotropic Chromonic Liquid Crystals (ChemPhysChem 3/2023)

The importance of and the difference between molecular versus structural core chirality of substances that form nanomaterials, and their ability to transmit and amplify their chirality to and within a surrounding condensed medium is yet to be exactly understood. Here we demonstrate that neat as well as disodium cromoglycate (DSCG) surface-modified cellulose nanocrystals (CNCs) with both molecular and morphological core chirality can induce homochirality in racemic nematic lyotropic chromonic liquid crystal (rac-N-LCLC) tactoids. In comparison to the parent chiral organic building blocks, D-glucose, endowed only with molecular chirality, both CNCs showed a superior chirality transfer ability. Here, particularly the structurally compatible DSCG-modified CNCs prove to be highly effective since the surface DSCG moieties can insert into the DSCG stacks that constitute the racemic tactoids. Overall, this presents a highly efficient pathway for chiral induction in an aqueous medium and thus for understanding the origins of biological homochirality in a suitable experimental system.     

Stable frustrated phases in chiral liquid crystals derived from optically active (R)- and (S)-3-ethylmercapto-2-methylpropionic acids

Highly optically pure (R)- and (S)-3-ethylmercapto-2-methylpropionic acids were synthesized by using optically active (D)- and (L)-2,10-camphorsultams as chiral auxiliaries, respectively. Their derivatives, (R)- and (S)-EMMPNmB (m=6-12), were prepared for investigation. Microscopic texture observations demonstrated that the materials possess three stable frustrated phases: BP, TGB_A* and TGB_C* phases. Interestingly, it was found that the N* phase behaves as an intermediary phase between BP and TGB_A* phases in a rather narrow temperature range (calc. 0.5-1.4°C). A study of the racemic mixture, (±)-EMMPNmB (m=10), indicated that the chirality of the molecule could suppress the formation of smectic phases in the heating process. An increase of alkyl chain length favoured the formation of the TGB phases particularly, in accompaniment with a change of TGB phases from monotropic to enantiotropic. Moderate maximum P _S values (calc. 14-19 nC cm^-2) and apparent tilt angle (calc. 20°) were obtained for the TGB_C* phase in a surface stabilized ferroelectric liquid crystal geometry.     

Rheological behavior and microstructure of 2,2′‐dioxy‐ 1,1′‐binaphthylphosphazene R/S random copolymer

Solutions of a binaphthoxy phosphazene copolymer (containing chiral 2,2′‐dioxy‐1,1′‐binaphthyl units with 50% R and S configurations distributed along the chains) in N‐methyl pyrrolidone were studied by means of continuous flow experiments and small amplitude oscillatory flow tests. A sudden viscosity decrease was observed in the polymer concentration range (39–40 wt %), evidencing a liquid‐crystalline polymer behavior. This has been confirmed by other rheological methods which have demonstrated that, for a sufficiently high concentration, the solutions of the binaphthoxy phosphazene copolymer give rise to a lyotropic system with formation of rigid rods (axial ratio of 10) stacked parallel to each other. The lyotropic properties of our binaphthoxy phosphazene copolymer are compatible with a regular helical structure, similar to that found for a homoleptic binaphthoxy phosphazene, which contains only S configuration. This suggests that the chains of 50% R/S binaphthoxy phosphazene copolymer are, in average, close to the strictly alternating R‐S copolymeric structure of the syndiotactic isomer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Bis-chelated imine-alkoxytitanium complexes: novel chiral dopants with high helical twisting power in liquid crystals

Enantiomerically and diastereomerically pure bis-chelated imine-alkoxytitanium complexes 6 and 7 have been synthesized and used as chiral dopants for converting nematic into cholesteric phases. The dopants were tested in mainly commercially available nematic liquid crystalline compounds or mixtures: LC1 (BASF), ZLI-1695 and ZLI-1840 (Merck), as well as N-(4-methoxybenzylidene)-4'-butylaniline (MBBA). The values of the helical twisting power (HTP) were determined by the Grandjean-Cano method. Exceptionally high helical twisting powers were obtained. Thus, the titanium complex 6 h displayed a HTP value of 740 microm(-1) in MBBA, the highest HTP value reported. The helical twisting power has been found to depend strongly on the structure of the nematic phase and the substitution pattern of the chiral ligand in the titanium complexes 6 and 7. Crystal structure analysis of 6 f confirmed the A,R,R configuration of the metal complex. The chiral imine ligands 4 and 5 were derived from the regioisomeric amino alcohols 1 and 2.