TY - JOUR
T1 - Functional molecules from single wall carbon nanotubes. Photoinduced solubility of short single wall carbon nanotube residues by covalent anchoring of 2,4,6-triarylpyrylium units
AU - Alvaro, Mercedes
AU - Aprile, Carmela
AU - Ferrer, Belen
AU - Garcia, Hermenegildo
PY - 2007/5/2
Y1 - 2007/5/2
N2 - Raw, micrometric HiPCO single wall carbon nanotube (SWNT) material was submitted to harsh acid oxidative treatment with a 3:1 H2SO 4/HNO3 mixture to give short residues of SWNT (s-SWNT, <200 nm length measured by TEM). s-SWNT was functionalized through the tip carboxylic groups by peptide bonds using 3-mercatopropanamine linkers that subsequently were reacted with 2,6-diphenyl-4-(4-vinylbiphenyl)pyrylium using azobis(isobutyronitrile) as a radical initiator. After purification by dialysis, the resulting s-SWNT having covalently linked through an ethylthiopropylamide tether the strong electron-transfer pyrylium photosensitizer (Py-sSWNT) was characterized by solution 1H NMR spectroscopy (observation of specific signals due to the heterocyclic protons). Emission spectroscopy shows that the fluorescence of 2,6-diphenyl-4-(4-dodecylthiobiphenyl)pyrylium (Py-SC12) tetrafluoroborate (a model compound to the tethered pyrylium moiety in Py-sSWNT) (λem 533 nm) is quenched by s-SWNT and vice versa that the emission of s-SWNT (λem 330 nm) is quenched by Py-SC12. Depending on the excitation wavelength, Py-sSWNT exhibits dual emission corresponding to each of the two moieties, but with much less intensity than each of the model components independently. Laser flash photolysis of model Py-SC12 allows detection of the triplet (λT-T 750 nm, τ 11.7 μs) and the much longer-lived pyrylium centered radical (λmax 525 nm, τ 147 μs). The latter species arises from photoinduced electron transfer from the sulfur atom, as the donor, to the pyrylium heterocycle in its electronic excited-state, as the electron acceptor. Laser flash photolysis (355 nm) of Py-sSWNT also allows detection of the pyrylium centered radical together with a broad absorption spanning from 200 to 500 nm and peaking at 280 nm. The latter band is absent in the laser flash photolysis of the model s-SWNT and was attributed to the electron hole localized on the nanotube moiety of Py-SWNT. The most remarkable effect of the steady-state irradiation is a 1 order of magnitude increase in the solubility of Py-sSWNT. According to TEM images this photoinduced solubility can be attributed to the debundling of the nanotubes due to photoinduced charge separation through the nanotube walls. In addition to exemplify how molecular compounds with photoresponsive properties can be derived from SWNT materials, the observation of photoinduced solubility can serve to develop SWNT layers suitable for photolithography patterning.
AB - Raw, micrometric HiPCO single wall carbon nanotube (SWNT) material was submitted to harsh acid oxidative treatment with a 3:1 H2SO 4/HNO3 mixture to give short residues of SWNT (s-SWNT, <200 nm length measured by TEM). s-SWNT was functionalized through the tip carboxylic groups by peptide bonds using 3-mercatopropanamine linkers that subsequently were reacted with 2,6-diphenyl-4-(4-vinylbiphenyl)pyrylium using azobis(isobutyronitrile) as a radical initiator. After purification by dialysis, the resulting s-SWNT having covalently linked through an ethylthiopropylamide tether the strong electron-transfer pyrylium photosensitizer (Py-sSWNT) was characterized by solution 1H NMR spectroscopy (observation of specific signals due to the heterocyclic protons). Emission spectroscopy shows that the fluorescence of 2,6-diphenyl-4-(4-dodecylthiobiphenyl)pyrylium (Py-SC12) tetrafluoroborate (a model compound to the tethered pyrylium moiety in Py-sSWNT) (λem 533 nm) is quenched by s-SWNT and vice versa that the emission of s-SWNT (λem 330 nm) is quenched by Py-SC12. Depending on the excitation wavelength, Py-sSWNT exhibits dual emission corresponding to each of the two moieties, but with much less intensity than each of the model components independently. Laser flash photolysis of model Py-SC12 allows detection of the triplet (λT-T 750 nm, τ 11.7 μs) and the much longer-lived pyrylium centered radical (λmax 525 nm, τ 147 μs). The latter species arises from photoinduced electron transfer from the sulfur atom, as the donor, to the pyrylium heterocycle in its electronic excited-state, as the electron acceptor. Laser flash photolysis (355 nm) of Py-sSWNT also allows detection of the pyrylium centered radical together with a broad absorption spanning from 200 to 500 nm and peaking at 280 nm. The latter band is absent in the laser flash photolysis of the model s-SWNT and was attributed to the electron hole localized on the nanotube moiety of Py-SWNT. The most remarkable effect of the steady-state irradiation is a 1 order of magnitude increase in the solubility of Py-sSWNT. According to TEM images this photoinduced solubility can be attributed to the debundling of the nanotubes due to photoinduced charge separation through the nanotube walls. In addition to exemplify how molecular compounds with photoresponsive properties can be derived from SWNT materials, the observation of photoinduced solubility can serve to develop SWNT layers suitable for photolithography patterning.
UR - http://www.scopus.com/inward/record.url?scp=34247868811&partnerID=8YFLogxK
U2 - 10.1021/ja0690520
DO - 10.1021/ja0690520
M3 - Article
AN - SCOPUS:34247868811
SN - 0002-7863
VL - 129
SP - 5647
EP - 5655
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 17
ER -