Abstract
The synthesis, characterization, thermal stability, optical spectroscopic, electronic structure, and second-order nonlinear optical (NLO) response of a series of donor-acceptor bis(salicylaldiminato)nickel(II) Schiff base complexes and the free ligand precursors are reported. The effect of the metal center in such complexes is manifold: it templates the formation of acentric molecular structures, imparts high thermal stability to the chelate ring, and both 'switches on' and enhances NLO response. Metal complexation imparts new linear optical spectroscopic features, having metal-to-ligand charge transfer character, which are responsible for the second-order nonlinearity. Moreover, the present synthetic strategy represents a novel route to inorganic NLO chromophores. Solution-phase hyperpolarizability values, deduced by electric field-induced second-harmonic-generation experiments are as high as -79 x 10-30 cm5 esu-1 (hω = 0.92 eV). Experimental linear and nonlinear optical features are fully consistent with INDO/SCI-SOS theoretical calculations. They provide a rationale for the NLO response of these materials and are attractive for designing new, highly efficient second-order nonlinear optical inorganic chromophores.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 9550-9557 |
| Number of pages | 8 |
| Journal | Journal of the American Chemical Society |
| Volume | 119 |
| Issue number | 40 |
| DOIs | |
| State | Published - 1997 |
Funding
We thank the RHIC Operations Group and RCF at BNL, and the NERSC Center at LBNL for their support. This work was supported in part by the HENP Divisions of the Office of Science of the U.S. DOE; the U.S. NSF; the BMBF of Germany; IN2P3, RA, RPL, and EMN of France; EPSRC of the United Kingdom; FAPESP of Brazil; the Russian Ministry of Science and Technology; the Ministry of Education and the NNSFC of China; IRP and GA of the Czech Republic, FOM of the Netherlands, DAE, DST, and CSIR of the Government of India; Swiss NSF; the Polish State Committee for Scientific Research; STAA of Slovakia, and the Korea Sci. and Eng. Foundation. for their support. This work was supported in part by the HENP Divisions of the Office of Science of the U.S. DOE; the U.S. NSF; the BMBF of Germany; IN2P3, RA, RPL, and EMN of France; EPSRC of the United Kingdom; FAPESP of Brazil; the Russian Ministry of Science and Technology; the Ministry of Education and the NNSFC of China; IRP and GA of the Czech Republic, FOM of the Netherlands, DAE, DST, and CSIR of the Government of India; Swiss NSF; the Polish State Committee for Scientific Research; STAA of Slovakia, and the Korea Sci. and Eng. Foundation.
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry