C₆₀-Containing Poly(1-phenyl-1-alkynes):  Synthesis, Light Emission, and Optical Limiting

Abstract

While polymerizations of 1-phenyl-1-propyne (PP) and 1-phenyl-1-butyne (PB) initiated by WCl 6 -Ph 4 Sn at room temperature yield small amounts of polymers (0.05-5.3%) with low molecular weights (M n 8000-15000) and high polydispersity indexes (PDI up to 109), addition of C 60 into the initiator mixture dramatically boosts its catalytic activity, producing polymers with high M n s (up to 171 000) and low PDIs (down to 2.2) in high yields (up to 99.5%). The resultant polymers are soluble, stable, and film-forming. GPC, IR, NMR, UV, and XRD analyses reveal that the polymers consist of polyacetylene chains and covalently bound C 60 cages (up to 9.1 wt %). Whereas photoluminescence of C 60 -containing polyPPs is faint, C 60 -containing polyPBs emit strong blue light (λ max ) 456 nm) readily observable with the naked eye under normal laboratory lighting. Compared with the parent C 60 , both two groups of the fullerene polyacetylenes show better optical limiting performance, and their THF solutions, with higher linear transmittance, attenuate the power of intense 532 nm optical pulses to lower saturation fluence.

Buckyballs

“…In 2000 the star shaped C 60 containing poly(1-phenyl-1-butyne) 16 turned out to be stable, and film-forming with a fullerene content of up to 9.1 wt%. NLO studies revealed that at 532 nm (Nd:YAG laser) 16 shows improved optical limiting performances compared to C 60 in solution at a linear transmission of 43% [104]. In the same year the side chain polyfullerene 17, prepared by Friedel-Crafts addition of C 60 and of a C 60 -derivative to a polycarbonate, also displayed good optical limiting properties [105].…”

Synthesis and Functionality of Substituted Polyacetylenes

“…Our group has done a pioneering work in wrapping CNTs with conjugated polymers. In 1999, our group successfully prepared PPA/CNT nanohybrid by in situ polymerization technique [81], and thereafter established a platform to prepare a series of PA/CNT and PA/C 60 nanohybrids by physical and chemical methods as shown in Scheme 1.8 [82,83].…”

“…The data for the parent forms, that is, PPA and C 60 , are given in the same figure for comparison [81,83]. When a THF solution of PPA is shot by the 8-ns, 532-nm laser light, the transmitted fluence linearly increases in the region of low incident fluence (linear transmittance 75%).…”

“…Similarly, the 72/C 60 also effectively limits the strong laser pulses. Compared to the solution of the parent C 60 , the 72/C 60 solutions show higher or same linear transmittance but lower saturation fluence [83]. Much effort has been devoted to the development of second-order NLO materials, particularly to the efficient translation of large molecular first hyperpolarizability to high second harmonic generation (SHG) coefficient (d 33 ).…”

The preparation and optical limiting properties of POSS-based molecular hybrid functional materials

“…Thus, the nonlinear refractive coefficients of the hybrids can be determined with equation(3). In accordance with the observed b and n 2 values, the third-order susceptibility c (3) value can be calculated with the following equation[32]:…”