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The authors report the near-IR sensitive star-shaped molecule [D-(CBz-TCP)3] containing bifunctional chromophores. A nonlinear optical active tricyanopyrroline-based plasticizer was also synthesized and introduced into the prepared molecular glass so as to control the glass transi-tion temperature of the photorefractive matrix. In a doped glass, they observed significantly enhanced photorefractive performances with regard to the asymmetric energy transfer and the diffraction efficiency at 830nm. In the presence of a small amount of (2,4,7-trinitro-9- fluorenylidene)malononitrile, they could demonstrate a very large net two beam coupling gain higher than 300cm−1 and a diffraction efficiency of 58%.