Third-order nonlinear optical properties of DA-salen-type nickel(II) and copper(II) complexes

• Type: Article in International Scientific Journal
• Date: 2006

Authors

Joao Tedim (Author) Other; Sonia Patricio (Author) Other; Rosa Bessada (Author) Other; Rui Morais (Author) Other; Carla Sousa (Author) Other; Manuel B Marques (Author) FCUP; Cristina Freire (Author) FCUP

Journal

Title: European Journal of Inorganic Chemistry

Vol. 2006

Pages: 3425-3433

ISSN: 1434-1948

Publisher: Wiley-Blackwell

Indexing

ISI Web of Knowledge - 38 Citations

Scopus - 38 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-004-HA6

DOI: 10.1002/ejic.200600017

Abstract (EN): Third-order nonlinear and linear optical properties of nickel(II) and copper(II) complexes with salen ligands, functionalised with electron donor/acceptor groups (DA-salen), have been investigated in solution by the Z-scan technique using an Nd:YAG laser (lambda(inc) = 1064 nm) and UV/Vis spectroscopy. The [M(DA-salen)] complexes exhibit positive nonresonant nonlinear refractive indexes (net) in the range 27.0-8.50 center dot 10(-21) m(2)W(-1) and nonlinear absorption coefficients (a(2)(I)) within the range 1.80-26.0 center dot 10(-17) mW(-1). The latter values correspond to less than 10% of the overall magnitude of the third-order susceptibility, vertical bar chi(3)vertical bar, which is the result of the absence of electronic transitions near lambda(inc) = 1064 nm. For the group of N-II complexes, the highest net values are exhibited by the complexes with aromatic diimine bridges and large pi-electron delocalisation, which leads to intense electronic charge-transfer bands (epsilon > 16000 mol(-1) dm(3) cm(-1)) in the region lambda = 275-500 nm. The complexes that exhibit charge-transfer bands near lambda(inc)/2 = 532 nm, also show the highest a(2)(I) values, a consequence of multiphoton absorption processes. For the group of Cult complexes, the highest net value is also observed by the complex that exhibits the most intense charge-transfer bands in the region lambda = 275-475 nm. Between Ni-II and Cu-II complexes with the same DA-salen ligands, those of copper show always higher net values, indicating that NLO responses can also be fine-tuned by the metal centre. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 9