Divergent route to the preparation of hybrid Pt–Fe 2,4,6-Tris(4-ethynyl)phenyl-1,3,5-triazine metallodendrimers for nonlinear optics

Maiti, Swarup K.; Jardim, Manuel G.; Rodrigues, João; Rissanen, Kari; Campo, Jochen; Wenseleers, Wim

http://hdl.handle.net/10400.13/2412

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Abstract(s)

The synthesis strategy for the preparation of novel platinum acetylide homometallic and heterobimetallic dendrimers (containing Fe as the other metal fragment) based on a 2,4,6-tris(4-ethynyl)phenyl-1,3,5-triazine core (3) is reported. All the dendrimer generations (G0−G2) were synthesized under copper-free conditions following a divergent route. The G0-Pt dendrimer (4) was synthesized using the 1,3,5-triazine core (3) and cis[Pt(PEt3)2Cl2] with a molar ratio of 1/4. The advantage of the current method is that diﬀerent dendrimers can be prepared by following the same procedure with only changes in the molar ratios of the reactants involved. For instance, when 3 reacts with 4 in a 4/1 molar ratio, the G1 dendrimer 7 is aﬀorded without the peripheral Pt moiety, but the G1 dendrimer with the peripheral Pt moiety (8) is formed when 3 reacts with 4 in a 1/3 molar ratio. On the other hand, the G2 dendrimer with a peripheral Pt moiety (9) is synthesized when 7 reacts with 4 in a 1/6 molar ratio. The heterobimetallic dendrimers were synthesized up to generation 1 by capping the corresponding Pt dendrimers with the ethynylferrocenyl group (EFC). The respective G0 (6)- and G1-capped (10) dendrimers were synthesized when EFC reacted with 4 and 8 in molar ratios of 9/1 and 18/1, respectively. Nonlinear optical (NLO) polarizabilities measured by hyper-Rayleigh scattering (HRS) have been evaluated for the core 3, for the G0 dendrimer 4, and for the G0 dendrimer capped with EFC (6). In spite of the fact that the stability of the higher generations in chloroform is too low to allow HRS measurements, the reported NLO results show a remarkable enhancement (plus 50%) upon capping the zero dendrimer generation (6), reﬂecting the importance of the introduction of electron donor organometallic capping groups in the hyperpolarizabilities of the resulting dendrimers.

Keywords

Preparation of hybrid Pt−Fe 2,4,6-Tris(4ethynyl)phenyl-1,3,5-triazine Metallodendrimers for nonlinear optics . Faculdade de Ciências Exatas e da Engenharia Centro de Química da Madeira

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http://hdl.handle.net/10400.13/2412

Citation

Maiti, S. K., Jardim, M. G., Rodrigues, J., Rissanen, K., Campo, J., & Wenseleers, W. (2013). Divergent Route to the Preparation of Hybrid Pt–Fe 2, 4, 6-Tris (4-ethynyl) phenyl-1, 3, 5-triazine Metallodendrimers for Nonlinear Optics. Organometallics, 32(2), 406-414.