Symmetrical and Nonsymmetrical Chromophores with Tröger’s Base Skeleton: Chiroptical, Linear, and Quadratic Nonlinear Optical Properties—A Joint Theoretical and Experimental Study

Abstract

We report on the novel chiral push-pull chromophores derived from 6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine (Tröger's base skeleton). The synthesis of symmetrical chromophores featuring two identical acceptors, as well as the synthesis of unsymmetrical chromophores featuring only one acceptor is given. Symmetrical chromophores were prepared in the enantiomerically pure form and their chiroptical properties were investigated. Second-order nonlinear optical (NLO) properties of new chromophores were investigated with the aid of hyper-Rayleigh scattering (HRS). The detailed theoretical analysis of the second-order NLO properties of the chromophores was also undertaken. The joint theoretical and experimental studies of chromophores derived from Tröger's base skeleton, in comparison with benchmark chromophores featuring a dimethylamino group as the donor, provided insight into the relationship between the structure of the new chromophores and their NLO properties.

Preparation and Enantioselectivity Binding Studies of a New Chiral Cobalt(II)porphyrin‐Tröger's Base Conjugate

“…To resolve racemic TB 2 we employed HPLC column Reprosil Chiral NR; an equivalent of Whelk O1, which is efficient for resolving various TB derivatives . We reached separation selectivity 1.16, and resolution 0.83.…”

Λ-shaped optoelectronic materials based on Tröger’s base

“…For example, Sergeyev's group reported the synthesis and optical properties of bi-chromophoric systems with two para-nitrophenyl or benzothiazolium acceptors, i.e., of 4 and 5 ( Figure 11) [50]. The results indicated that the combination of donor--acceptor design and the inherent chirality of the molecule hold considerable promise as a scaffold for nonlinear optics (NLO) chromophores.…”

Prevention of postoperative adhesion formation by individual and combined administration of 4 per cent icodextrin and dimetindene maleate (Br J Surg 2009; 96: 1476–1483)

“…Organic light‐emitting diodes (OLEDs) fabricated with these TB analogues show high brightness, high efficiency, and low turn‐on voltage. Benzothiazolium‐ and para ‐nitrophenyl‐derived TB analogues 114 and 115 , respectively (Figure 33), show second‐order nonlinear optic properties, the former being the more active 89,124…”