Nitrocalix [4]arenes as Molecules for Second‐Order Nonlinear Optics

Abstract

The frequency‐doubling of 820nm laser light is one of the properties of a series of nitrocalix‐[4]arenes making them suitable, in principle, for the construction of a blue laser. Derivative 1 is the most promising, since it displays the greatest hyperpolarizability and the largest dipole moment and is stable as a film in a polymer matrix for long periods.

Quadratic nonlinear optical properties of correlated chromophores: cyclic 6,6′-dinitro-1,1′-binaphthyl-2,2′-ethers

“…In contrast to their (mono-)dipolar and octopolar counterparts, the multi-dipolar molecules combine several charge-transfer units within a single molecule and hence can provide larger hyperpolarizabilities, without the classic bathochromic shift of the charge transfer band. Apart from the calixarenes [2], the 6,6'-disubstituted derivatives of binaphthol are emerging as useful multi-dipolar molecules [3,4]. In this Letter we present new experimental results on hyper-Rayleigh scattering (HRS) and electric-fieldinduced second-harmonic-generation (EFISHG) measurements on chiral 6,6'-disubstituted binaphthyl ethers in which the dihedral angle is varied by bridging the two oxygen atoms with alkyl chains of different lengths (Fig.…”

Selective nitration of calix[4]arenes that easily gave inherently chiral calix[4]arenes

“…To get calixarene bearing nitro groups only on certain phenol rings, calixarene was selectively etherified in advance at lower rim, and then it was selectively nitrated on the phenol ring(s) without etherification [18][19][20][21]. To prepare an expected nitrocalixarene or nitrogen-containing calixarene by direct nitration of calixarene without selective etherification in advance is very rare, [22,23] although directly selective nitration is a more concise method because of less reaction steps. Here we report that the proximally dietherified calix [4]arene at lower rim was selectively nitrated to give mononitrocalix [4]arene, dinitrocalix [4]arene and trinitrocalix [4]arene respectively under different reaction conditions just by recrystallization.…”

Nonlinear Optical Properties in Calix[n]arenes: Orientation Effects of Monomers

“…It would thus be very interesting to ask how the individual dipoles of the chromophores interact in such a multi-molecular assembly and how such interactions and molecular properties translate into controlling the overall NLO properties of the calix[n]arenes. Although there has been a substantial effort in NLO characteristics of calix[n]arenes, [12] a proper understanding from a molecular viewpoint is clearly missing. To our knowledge, there has been only one work to model the NLO properties of these systems, [13] which, however, addresses none of the issues discussed above.…”