ORGN 758 |
| We present a quantum-chemical analysis of the central metal ions effect on first hyperpolarizabilities and two photon absorption of a series of push-pull porphyrins whose synthesis and NLO properties has been reported earlier (J. Am. Chem. Soc. 127, 9710, 2005). The effect of the donor-acceptor strengths and conjugation path lengths has been evaluated to demonstrate the engineering guidelines for enhancing molecular optical non-linearity. The molecular geometries are obtained via B3LYP/6-31G (d,p) level optimization including SCRF/PCM approach, while the dynamic NLO properties are calculated with the ZINDO/CV method including solvent effects. It has been observed that the first hyperpolarizabilities can be greatly enhanced by changing the central metal ions and increasing the strengths of the electron donor/acceptor. It is found that the CT transition between the metal ion's d orbital and the macrocycle p orbital plays an important role on first hyperpolarizability of metal porphyrins. Our data suggest a new approach to enhance nonlinear optical properties of porphyrin materials. Importance of our results on the design of electro-optic materials will be discussed |
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Materials, Devices, and Switches
8:00 AM-12:00 PM, Thursday, March 29, 2007 McCormick Place Lakeside -- Room E450 A/B, Level 4, Oral
Division of Organic Chemistry |