Induced circular dichroism effects

C-O-C groups rather than connected with the CH2 subunits of the dendritic branches. The VCD results support the explanation of the observed induced circular dichroism effect as a consequence of the chiral arrangement of the inherently achiral benzene rings within the dendritic branches that was induced by the chiral center. 

Photochemically Triggered Induced Circular Dichroism in Liposomes When an optically inactive chromophore is subject to the effect of optically active environment, optical activity may be induced at the absorption wavelength of the optically inactive chromophore. This phenomenon of induced circular dichroism(ICD) is often observed in polypeptides bearing various achiral chromophores on the side chain( ). The strong chiral environment caused by the peptide helix structure is responsible for this. Distance from, and orientation to, the chiral field decide the degree of ICD appearing on the achiral chromophore. 

The induced circular dichroism and Cotton effect have been investigated for quaternary ammonium ions with N anchored on an asymmetric C, when hosted in calix[n]arene molecules (215, n = 4, 6, 8)430. 

The absolute configuration of chiral nonracemic compounds can be established by forming a complex which can bind to the axial position of [Rh2(02CCF3)4] and thus induce circular dichroism within its electronic absorption bands. This method works well for chiral secondary alcohols and monoolefins. For these compounds tentative rules were proposed, which correlate the configuration of the starting materials with the sign of certain Cotton effects of their complexes178. 

As chiral molecules, CD hosts are one of the best chiral selectors [23]. They can also induce circular dichroism signal in an achiral guest. As shown by Zhang and Nau [24] for the complexes of p-CDwith bicyclic azaalkanes 290 or 291, this effect may allow one to determine the orientation of the latter molecule in the CD cavity. An interesting example of the influence of 11 on the guest conformation was reported by Brett and coworkers [25]. They have shown that p-amino-/ -nitrobiphenyl 292, which is planar in the solid state, becomes nonplanar in the solid state complex with 3-CD. 

ICD induced circular dichroism NMR nuclear magnetic resonance NOE nuclear Overhauser effect TTF tetrathiafulvalene... 

In a study of chiral dipeptide [2]rotaxanes it was found that the presence of an intrinsically achiral benzylic amide macrocycle near to the chiral center could induce an asymmetric response in the aromatic ring absorption bands [62], This induced circular dichroism (ICD) effect was stronger in apolar solvents (Fig. 9), where intercomponent interactions are maximized, showing a direct relationship to the tightness with which the macrocycle binds the chiral thread. Computer simulations showed that chirality is transmitted from the amino acid asymmetric center on the thread via the achiral macrocycle to the aromatic rings of the achiral C-terminal stopper. 

Spada GP (2008) Alignment by the convective and vortex flow of achiral self-assembled fibers induces strong circular dichroism effects. Angew Chem Int Ed Engl 47 636-638... 

The induced circular dichroism (ICD) spectra of five /3-cyclodextrin derivatives containing a benzisoselenazol-3(27T)-one moiety show two positive Cotton effects at ca. 232-246 and 259-264 nm. This indicates that the benzisoselenazolone moiety lies outside the chiral cavity of /3-cyclodextrin, and both of the transition moments may be perpendicular to the axis of the /3-cyclodextrin cavity. In contrast, the ICD spectra of other /3-cyclodextrin derivatives display one negative Cotton effect at 229 nm and a positive Cotton effect at 248 nm. It can be inferred that the benzisoselenazolone moiety is located inside the chiral cavity of /3-cyclodextrin <2002HCA9>. 

Several physical methods have been employed to ascertain the existence and nature of ICs infrared (IR) absorption spectroscopy nuclear magnetic resonance (NMR) spectroscopy,14 including JH nuclear Overhauser effect (NOE) difference spectroscopy, H 2-D rotating-frame Overhauser effect spectroscopy (2-D ROESY),15 and solid-state 13C cross-polarization/magic angle spinning (CP/MAS) spectroscopy 16 induced circular dichroism (ICD) absorption spectroscopy 17 powder and singlecrystal X-ray diffraction 18 and fast atom bombardment mass spectrometry (FAB MS). 

MOR, also known as Faraday effect) [21], i.e. an induced rotation of the plane of polarization (or circular birefringence). The other is an induced circular dichroism referred to as magnetic-circular dichroism (MCD) [21, 22, 132, 133]. 

The u.v. and c.d. spectra of (364 R = Me, Et, Pr, Bu , or PhCH2) in EtOH and in iso-octane have been reported.The chiroptical properties of the oxaziridine chromophore were generally characterized by a positive pattern at 190—350 nm. The notable exception to this was a clear negative Cotton effect for (364 R = Pr ). The seemingly anomalous behaviour of this compound was interpreted in terms of the possible existence of solvation equilibria and conformational rotamers about the N—CHMe2 bond. The relatively new technique of Liquid-Crystal-Induced Circular Dichroism (LCICD) has been used in the... 

Induced circular dichroism. Induced circular dichroism is observable for electronic transitions of an achiral molecule when, for example, it is associated in the form of a coordination complex with a chiral molecule. In the example given by Stang of a tetranuclear platinum complex where two achiral fragments are linked by two S,S)-tartrate anions (2.36) (Figure 2.59), a Cotton effect is observed for the transitions of the achiral anthracene unit. 

On the other hand, it was reported that either several reactions could not be reproduced or no asymmetric effect was found Negative results in several works were explained by the large steps of the helix in the structure of cholesteric liquid crystals (300-400 nm) and by the absence of chirodiastaltic interaetion with the small molecules of the substrates. In the case of large molecules of complicated stereostmctures it was possible to wait for the appearance of such interactions as revealed by the appearance of induced circular dichroism (ICD) in the absorption bands of chromophors of components and products of the reaction. 

Cationic zinc porphyrins are well-known DNA interca-lators. Interestingly, however, they are not effective for Z-DNA since binding destabilizes the left-handed helix and causes it to revert to the B state. However, the simple modification of coordinating water in an axial position of a Zn porphyrin prevents intercalation, thereby obviating the reversion to the B-form. This was a feature that was exploited by Purrello and coworkers. They found that at a micromolar concentration of porphyrin, an intense bisig-nate induced circular dichroism (ICD) signal was seen in the case of Z-DNA only a small ICD signal was seen in the case of B-DNA. 

Liquid crystal induced circular dichroism (LCICD) examines the differential absorption of circularly polarized radiation by an achiral solute oriented in a cholesteric liquid crystal. The circular dichroism results from an induced Cotton effect in the achiral solute due to the macroscopic chirality of its ordering in the helical solvent matrix. The effect has been shown theoretically to arise... 

At the outset of our own work there seemed to be considerable scope for synthesising alternative polymer-supported catalysts in order to explore the effectiveness of a wider range of chiral structures and also to provide a wider context in which the earlier results might be viewed. Our approach, however, has remained essentially a trial and error one, although more recently we have embarked upon a more rational, though longer term, examination of the problem using induced circular dichroism observed in achiral anions bound to chiral cations ... 

A circular dichroism signal may be observed also for achiral molecules immersed in chiral environments (for example, dissolved in a chiral solvent or complexed by chiral receptors) [6]. This effect is known as induced circular dichroism (ICD) and is generally very weak [7]. ICD spectroscopy is frequently used in supramolecular chemistry to smdy the complexation of an achiral guest by a chiral host [8]. An example of this kind is represented by the association of optically inactive organic chromophores with cyclodextrins, that are macrocyclic receptors possessing a chiral cavity [9, 10]. 

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