[RuII(FT)(bipy)(NO)][PF6]3 [FT is the electron‐rich 4′‐(2‐fluorenyl)‐2,2′:6′,2′′‐terpyridine ligand and bipy is 2,2′‐bipyridine] is synthesized and characterized. It crystallizes in the triclinic P1 space group [a = 9.5362(2) Å, b = 10.3946(4) Å, c = 22.5701(8) Å, α = 94.7400(10)°, β = 94.9400(10)°, γ = 101.0680(10)]. A photochemical study is presented in comparison with that of the parents cis(Cl,Cl)‐[RuII(FT)Cl2(NO)][PF6] and trans(Cl,Cl)‐[RuII(FT)Cl2(NO)][PF6]. The three derivatives release nitric oxide (·NO) under irradiation at λ = 405 nm with respective quantum yields of 0.06, 0.31, and 0.10. Their two‐photon absorption (TPA) cross‐sections (σTPA) were investigated by the Z‐scan technique on related derivatives in which two hexyl chains were introduced to improve their solubility while their spectroscopic properties remained almost unaffected. The resulting σTPA values of 100 GM at λ = 800 nm are in the window of transparency for human tissues, and the bipyridine‐based complex exhibits a slight tendency for higher efficiency. The replacement of the [RuII(Cl)2(NO)] core by [RuII(bipy)(NO)] provides a much simpler synthesis, and the TPA‐induced ·NO‐release capabilities are in the same range of magnitude. Therefore, it is envisioned that ·NO donors of greater complexity with several metal centers could be investigated in future.
A ruthenium-nitrosyl derivative of formula [Ru II (CzT)(bipy)(NO)](PF 6 ) 3 [CzT = 4′-(N-ethylcarbazol-3-yl)-2,2′:6′,2′′-terpyridine, bipy = 2,2′-bipyridine] has been synthesized and fully characterized, and compared with the previously reported [Ru II (FT)(bipy)(NO)](PF 6 ) 3 complex [FT = 4′-(9,9-dihexyl-9H-fluoren-2-yl)-2,2′:6′,2′′-terpyridine]. Additionally, the Xray crystal structure of [Ru II (CzT)(bipy)(NO 2 )](PF 6 ), the precursor of [Ru II (CzT)(bipy)(NO)](PF 6 ) 3 , is reported. The presence of a ter-
The synthesis, crystal and electronic structures, and one- and two-photon absorption properties of two quadrupolar fluorenyl-substituted tetraphenyl carbo-benzenes are described. These all-hydrocarbon chromophores, differing in the nature of the linkers between the fluorenyl substituents and the carbo-benzene core (C-C bonds for 3 a, C-C=C-C expanders for 3 b), exhibit quasi-superimposable one-photon absorption (1PA) spectra but different two-photon absorption (2PA) cross-sections σ2PA. Z-scan measurements (under NIR femtosecond excitation) indeed showed that the C≡C expansion results in an approximately twofold increase in the σ2PA value, from 336 to 656 GM (1 GM = 10(-50) cm(4) s molecule(-1) photon(-1)) at λ = 800 nm. The first excited states of Au and Ag symmetry accounting for 1PA and 2PA, respectively, were calculated at the TDDFT level of theory and used for sum-over-state estimations of σ2PA(λi), in which λi = 2 hc/Ei, h is Planck's constant, c is the speed of light, and Ei is the energy of the 2PA-allowed transition. The calculated σ2PA values of 227 GM at 687 nm for 3 a and 349 GM at 708 nm for 3 b are in agreement with the Z-scan results.
Two-photon
excitation in the near-infrared (NIR) of colloidal nanocrystalline
silicon quantum dots (nc-SiQDs) with photoluminescence also in the
NIR has potential opportunities in the field of deep biological imaging.
Spectra of the degenerate two-photon absorption (2PA) cross section
of colloidal nc-SiQDs are measured using two-photon excitation over
a spectral range 1.46 < ℏω < 1.91
eV (wavelength 850 > λ > 650 nm) above the two-photon
band gap E
g
(QD)/2, and at a
representative
photon energy ℏω = 0.99 eV (λ
= 1250 nm) below this gap. Two-photon excited photoluminescence (2PE-PL)
spectra of nc-SiQDs with diameters d = 1.8 ±
0.2 nm and d = 2.3 ± 0.3 nm, each passivated
with 1-dodecene and dispersed in toluene, are calibrated in strength
against 2PE-PL from a known concentration of Rhodamine B dye in methanol.
The 2PA cross section is observed to be smaller for the smaller diameter
nanocrystals, and the onset of 2PA is observed to be blue shifted
from the two-photon indirect band gap of bulk Si, as expected for
quantum confinement of excitons. The efficiencies of nc-SiQDs for
bioimaging using 2PE-PL are simulated in various biological tissues
and compared to efficiencies of other quantum dots and molecular fluorophores
and found to be comparable or superior at greater depths.
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