The 1D character of single-walled carbon nanotubes (SWCNT) combined with their mechanical robustness, chemical inertness and wide range of diameters makes them ideal nanocontainers for various molecules. Here we show that by encapsulating elongated dipolar molecules in the 1D internal channel of SWCNTs, Coulomb interactions naturally favour a polar head-to-tail alignment of the molecular dipoles, resulting in a cooperative enhancement of directional properties, such as the dipole moment and the second-order nonlinear optical (NLO) response.[1]  This principle is demonstrated for a prototypical dipolar molecule encapsulated in various SWCNT samples. The encapsulation is evidenced by extensive wavelength-dependent fluorescence-excitation and resonant Raman experiments on bile-salt solubilised dye-filled SWCNTs[2], revealing the effect of encapsulation on the vibrational and electronic properties of the SWCNTs and the encapsulated molecules.[3-6] The polar alignment is demonstrated by wavelength-dependent hyper Rayleigh scattering experiments (HRS)[7-9] (i.e. second harmonic light scattering). The newly synthesized organic nanohybrids possess a giant total dipole moment and NLO response, corresponding to ~70 identically aligned molecules (HRS intensity scaling quadratically with this number). These nanohybrids form solution processible building blocks highly interesting for the development of electro-optic modulators and switches.

References

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