Dendron Decorated Platinum(II) Acetylides for Optical Power Limiting

Abstract

The effect of dendritic substituents on a nonlinear optical chromophore for optical power limiting (OPL) has been investigated. Synthesis and characterization of bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II) with dendritic end groups are described. Polyester dendrimers up to the fourth generation were grown divergently using the anhydride of 2,2-bis(methylol)propionic acid (bis-MPA). The introduction of the dendritic moieties onto the NLO chromophore enables further processing of the materials using polymeric and related techniques. OPL measurements performed at 532, 580, and 630 nm show that the OPL properties improve with increasing size of the dendritic substituent. It is also shown that the addition of the dendrons increase the OPL as compared to the nondecorated bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II). By use of femtosecond z-scan measurements carried out at different pulse-repetition frequencies, it is shown that the two-photon absorption cross section is ∼10 GM. Using pulse repetition frequencies (100 kHz-4.75 MHz) so that the time between the pulses is comparable with the triplet excited lifetime, the z-scans become dominated by excited-state absorption of excited triplet states.

Optical Properties of Hybrid Organic‐Inorganic Materials and their Applications

“…For instance the platinum(II) square-planar complex trans-[P(n-Bu) 3 ] 2 Pt[(C C-p-C 6 H 4 -C C-p-C 6 H 5 ] 2 [326,346,347] was reported for efficient nonlinear absorption in solution, [326,[346][347][348] and series of derivatives were prepared with improved properties. [294,[349][350][351][352][353][354][355][356][357][358] The use of PMMA monoliths hosting platinum derivatives was an efficient route towards OPL materials. [278,359] The measured linear transmissions were nearly 90% in the visible and NLO properties were maintained in the solid.…”

Efficient Nonlinear Absorbing Platinum(II) Acetylide Chromophores in Solid PMMA Matrices

“…[14] Platinum(II) acetylides on the other hand, are only slightly colored and well known to possess strong excited state absorption, [21][22][23][24][25] giving rise to efficient nonlinear absorbing properties. [15] Previous results presented by a number of authors, [21,[25][26][27][28][29][30][31] demonstrate the fundamental photophysical properties of platinum (II) acetylides and discuss their potential use in optical power limiting (OPL) applications.…”

Advances in the Elegance of Chemistry in Designing Dendrimers

“…[89] Since then, several examples in the literature have been presented by the groups of Takahashi, [90] Leininger, [91] Humphrey, [92] and others. [93] Takahashi and coworkers reported the synthesis of organo-platinum dendrimers of different sizes based on Ptacetylide linkages using convergent, divergent, or a combination of the two synthetic methodologies (Figure 21). [90] In general, the procedure relied on using the Cu I -catalyzed coupling reaction of Pt-Cl groups and terminal acetylenes.…”