Synthesis Structure and Second Harmonic Efficiencies of MAP Anal-ogues

Abstract

An attempt to improve the second harmonic generation (SHG) efficiency of MAP (methyl (2,4-dinitrophenyl)aminopropanoate) by modifying the substituents on the amino group of MAP is described. Several MAP analogues have been prepared using optically active amino acids alanine, phenylalanine and serine, and their SHG efficiencies measured. None of the MAP analogues exhibited SHG efficiencies as high as that of MAP. X-ray crystal structures of three MAP analogues have been determined. In the crystal structures of two of them, which were the derivatives of phenylalanine, two crystallographically-independent molecules existing in the asymmetric unit are aligned almost antiparallel. These structures are consistent with the very low SHG efficiencies of these compounds. On the other hand, the crystal structure of a serine derivative reveals substantial alignment of the dinitroaniline chromophore along the polar axis. However, the angle of 86.2-degrees between the molecular charge tranfer axis and the polar axis of the crystal is still far away from the optimum value of 54.74-degrees for the phase-matchable SHG. The structure is consistent with the SHG efficiency of this compound which is much higher than those of the phenylalanine derivatives but still lower than that of MAP. This study demonstrates the importance of the orientation of molecules in the crystal lattice in determining secod-order nonlinear optical properties of crystalline materials.