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First Example of Nonlinear Optical Materials Based on Nanoconjugates of Sandwich Phthalocyanines with Quantum Dots
Author(s) -
Oluwole David O.,
Yagodin Alexey V.,
Mkhize Nhlakanipho C.,
Sekhosana Kutloano E.,
Martynov Alexander G.,
Gorbunova Yulia G.,
Tsivadze Aslan Yu.,
Nyokong Tebello
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604401
Subject(s) - homoleptic , covalent bond , phthalocyanine , quantum dot , materials science , europium , thioglycolic acid , chemistry , nanotechnology , crystallography , luminescence , optoelectronics , organic chemistry , metal , metallurgy
We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double‐ and triple‐decker europium(III) complexes 2 and 3 with the A 3 B‐type phthalocyanine ligand (2,3‐bis[2′‐(2′′‐hydroxyethoxy)ethoxy]‐9,10,16,17,23,24‐hexa‐ n ‐butoxyphthalocyanine 1 ) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid‐capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low‐symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open‐aperture Z‐scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double‐ and triple‐decker Eu III octa‐ n ‐butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide‐capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π‐electron system upon moving from double‐ to triple‐decker complexes significantly improves the OL characteristics, making the low‐symmetry triple‐decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm −2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double‐ and triple‐decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.