Influence of the Central Metal Ion on Nonlinear Optical and Two-Photon Absorption Properties of Push−Pull Transition Metal Porphyrins Export

@article{citeulike:5884018, abstract = {PMID: 18302349 We present a quantum-chemical analysis of the central metal ion's effect on first hyperpolarizabilities and two-photon absorption (TPA) cross sections at the infrared region of a series of pushpull porphyrins whose synthesis and NLO properties have been reported earlier (J. Am. Chem. Soc. 2005, 127, 9710). The molecular geometries are obtained via the B3LYP/6-31G(d,p) level optimization including SCRF/PCM approach, and the NLO and TPA properties are calculated with the ZINDO/CV method including solvent effects. It is found that the CT transition between the metal ion's d orbital and the macrocycle pi orbitals plays an important role on NLO and TPA properties of metal porphyrins. Our data suggest a new approach to enhance TPA properties of porphyrin materials. We also present a quantum-chemical analysis on porphyrin dimers and trimers to understand the relationship between structural and collective NLO properties. It has been observed that beta values can be improved about an order of magnitude and TPA properties can be enhanced by 2 orders of magnitude by the formation of a trimer. The importance of our results with respect to the design of photonic and photodynamic therapy materials have been discussed.}, author = {Ray, Paresh C. and Bonifassi, P. and Leszczynski, J.}, citeulike-article-id = {5884018}, citeulike-linkout-0 = {http://dx.doi.org/10.1021/jp7096179}, citeulike-linkout-1 = {http://pubs.acs.org/doi/abs/10.1021/jp7096179}, day = {1}, doi = {10.1021/jp7096179}, journal = {The Journal of Physical Chemistry A}, keywords = {absorption, citedby4, ion, nonlinear, optical, porphyrins, two-photon}, month = {April}, number = {13}, pages = {2870--2879}, posted-at = {2009-10-04 02:06:22}, priority = {2}, title = {Influence of the Central Metal Ion on Nonlinear Optical and Two-Photon Absorption Properties of Push−Pull Transition Metal Porphyrins}, url = {http://dx.doi.org/10.1021/jp7096179}, volume = {112}, year = {2008} }

TY - JOUR ID - citeulike:5884018 L3 - citeulike-article-id:5884018 N2 - PMID: 18302349 We present a quantum-chemical analysis of the central metal ion's effect on first hyperpolarizabilities and two-photon absorption (TPA) cross sections at the infrared region of a series of pushpull porphyrins whose synthesis and NLO properties have been reported earlier (J. Am. Chem. Soc. 2005, 127, 9710). The molecular geometries are obtained via the B3LYP/6-31G(d,p) level optimization including SCRF/PCM approach, and the NLO and TPA properties are calculated with the ZINDO/CV method including solvent effects. It is found that the CT transition between the metal ion's d orbital and the macrocycle pi orbitals plays an important role on NLO and TPA properties of metal porphyrins. Our data suggest a new approach to enhance TPA properties of porphyrin materials. We also present a quantum-chemical analysis on porphyrin dimers and trimers to understand the relationship between structural and collective NLO properties. It has been observed that beta values can be improved about an order of magnitude and TPA properties can be enhanced by 2 orders of magnitude by the formation of a trimer. The importance of our results with respect to the design of photonic and photodynamic therapy materials have been discussed. IS - 13 JF - The Journal of Physical Chemistry A EP - 2879 TI - Influence of the Central Metal Ion on Nonlinear Optical and Two-Photon Absorption Properties of Push−Pull Transition Metal Porphyrins VL - 112 SP - 2870 KW - absorption KW - citedby4 KW - ion KW - nonlinear KW - optical KW - porphyrins KW - two-photon AU - Ray, Paresh AU - Bonifassi, P AU - Leszczynski, J PY - 2008/04/01/ UR - http://dx.doi.org/10.1021/jp7096179 ER -