Linear and nonlinear optical properties of triphenylamine-functionalized C₆₀: insights from theory and experiment

Abstract

In the present study we report on the linear and nonlinear optical properties of C(60)-triphenylamine (TPhA) hybrids. The synthesized materials were prepared following the 1,3-dipolar cycloaddition of azomethine ylides onto the skeleton of C(60) forming the TPhA-based monoadduct, equatorial bis-adduct and dumbell C(60). Complementary spectroscopic techniques, such as NMR, MALDI-TOF-MS, and ATR-IR are applied for the structural characterization of the hybrid materials, while intermolecular electronic interactions are investigated by UV-Vis measurements. In all considered cases, C(60) serves as an acceptor while the triphenylamine unit is chosen as a donor. In order to investigate the dependence of the second-order hyperpolarizability on the architecture of the systems (D-A, A-D-A) we use a Z-scan technique employing 532 nm, 35 ps laser pulses. We have found that the total second-order hyperpolarizability of the C(60)-TphA-C(60) system is several times larger than that of TPhA-C(60). The results of experimental measurements are supported by quantum-chemical calculations.

Thermochemical stabilities, electronic structures, and optical properties of C56X10 (X = H, F, and Cl) fullerene compounds

“…It is well known that halofullerenes are excellent electron acceptors with potential photonic/photovoltaic applications. As their analogs, similar application could be expected for C 56 F 10 and C 56 Cl 10 .…”

“…However, as three different compounds, the extents of localization of p electron density are slightly different. 10 , respectively. In contrast, the contributions from X atoms to FMOs of C 56 X 10 are so small that can be neglected.…”

“…[3][4][5][6][7][8] Like organic compounds, fullerenes possess highly delocalized p conjugated electrons, which is the main origin for large linear and nonlinear optical (NLO) responses. 9 Thus far, considerable experimental and theoretical studies are directed toward investigating on the electronic and NLO properties of higher fullerenes (e.g., C 60 , C 70 , C 76 , and C 84 ) and their endo-, hetero-, and exo-derivatives, [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] such as Li@C 60 , 18 M@C 74 (M 5 La, Ca, and Ba), 19-21 C 59 Si and C 58 Si 2 , 22 and Fe(g 5 -C 55 X 5 ) 2 (X 5 CH, N, B), 23 together with ferrocene and porphyrin derivatives of C 60 . 24,25 However, smaller fullerenes C n (n \ 60), because of the enhanced local strains and the resonance destabilization pertaining to adjacent pentagons, which violate the well-known isolated pentagon rule (IPR), 26 are predicted to be neither stable in structures nor isolable in experiments.…”

Experimental and theoretical studies of the second- and third-order NLO properties of a semi-organic compound: 6-Aminoquinolinium iodide monohydrate

“…Briefly, in the Z-scan technique, the transmittance of a sample is measured as it moves along the propagation direction of a focused Gaussian laser beam, therefore experiencing different intensity at each position. By fitting the experimental data according to equations which can be found in the literature [26,27], the nonlinear absorption parameter, β, the Im χ (3) and Im γ values can be obtained. Before the measurements, we performed a calibration of the nonlinear absorption setup using samples of C60 fullerene, which is a well known optical limiter.…”

“…The nonlinear absorption of the title compound was investigated with "open-aperture" Z-scan measurements employing 532 nm, 35 ps laser pulses, following the procedure described elsewhere [26,27]. Briefly, in the Z-scan technique, the transmittance of a sample is measured as it moves along the propagation direction of a focused Gaussian laser beam, therefore experiencing different intensity at each position.…”