Intramolecular charge-transfer interaction

Based on the fundamental dipole moment concepts of mesomeric moment and interaction moment, models to explain the enhanced optical nonlinearities of polarized conjugated molecules have been devised. The equivalent internal field (EIF) model of Oudar and Chemla relates the j8 of a molecule to an equivalent electric field ER due to substituent R which biases the hyperpolarizabilities (28). In the case of donor-acceptor systems anomalously large nonlinearities result as a consequence of contributions from intramolecular charge-transfer interaction (related to /xjnt) and expressions to quantify this contribution have been obtained (29). Related treatments dealing with this problem have appeared one due to Levine and Bethea bearing directly on the EIF model (30), another due to Levine using spectroscopically derived substituent perturbations rather than dipole moment based data (31.) and yet another more empirical treatment by Dulcic and Sauteret involving reinforcement of substituent effects (32). 

E. Tertiary Amines as Donors in Intramolecular Charge Transfer Interaction... 

Furo T, Mori T, Wada T, Inoue Y (2005) Absolute configuration of Chiral [2.2]paracyclo-phanes with intramolecular charge-transfer interaction. Failure of the exciton chirality method and use of the sector rule applied to the cotton effect of the CT transition. J Am Chem Soc 127 7995-8006 and 1638... 

For investigations of intramolecular charge-transfer interactions, donor- and acceptor-substituted cyclophanes are particularly well suited, since they allow for wide variation of substitutents. Interplanar-distance and orientation of aromatic planes can be tuned by choosing appropriate bridge lengths. Synjanti conformational preferences have an additional influence on charge-transfer interactions. Severals studies of this kind were undertaken by Staab et al. 17,34-36]. In usually good yields they synthesized methoxy-sutetituted [2.2]meta- and metaparacyclo-phanes with bromo-, cyano-, nitro-, or ester-substituents. In the case of methoxy-substituted substrates, often a few percent of quinoid by-products do form, e.g., 40, 41, and 44, which have been isolated in some cases. 

A simple synthesis of pyrazolo[4, 5 ][60]fullerenes from pyrazolyl hydrazones with [60]fullerene was achieved with microwave irradiation evidence of intramolecular charge-transfer interaction was shown <1999TL1587>. Novel C6o-fused isoxazolines have been synthesized from 1,3-dipolar cycloadditions of pyrazole nitrile oxides to Ceo under thermal or microwave irradiation <1999T4889>. A new triad based on pyrazolino[60]fullerene and a conjugated... 

Huang W, Han CD (2012) Synthesis and intramolecular charge-transfer interactions of a donor-acceptor type polymer containing ferrocene and TCNAQ moieties. Macromolecnles 45 4425 428... 

Wagner, P. J. and Lindstrom, M. J., Intramolecular charge-transfer interactions in triplet keto sulfides, J. Am. Chem. Soc., 109, 3057,1987. 

In high P push-pull ir-organic chromophores of interest in most NLO studies, the second-order response was assumed to be the sum of additive portions and the intramolecular charge-transfer interaction between acceptor and donor, for example ... 

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