Higher-order triplet interaction in energy-level modeling of excited-state absorption for an expanded porphyrin cadmium complex

McKerns, Michael; Sun, Wenfang; Lawson, Christopher M.; Gray, Gary M.

doi:10.1364/josab.22.000852

Cited by 14 publications

(8 citation statements)

References 24 publications

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“…A major application of the novel polyphosphonates containing 2,2′‐bithienyl‐5‐yl substituents ( 4O , 4S , 4Se ) is for optical power limiting (OPL) applications in the violet‐blue spectral region. Materials exhibiting large third‐order nonlinear absorptions (NLAs) have been studied extensively due to their ability to be used for OPL applications such as eye and optical sensor protection . Research in developing “smart” OPL materials has increased in recent years due to the fact that frequency‐fixed filters are ineffective in protecting optical systems from damage from wavelength‐tunable laser threats, which have recently become more readily available .…”

Section: Resultsmentioning

confidence: 99%

Synthesis, thermal analysis, and linear and nonlinear optical characterization of substituted polyphosphonates derived from 1,12-dodecanediol

Freeman

Martin

Totsch

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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The syntheses of a series of substituted polyphosphonates of the type [OP(X)(Ar)O(CH2)12]n (X = O, S, Se; Ar = phenyl, 2,2′‐bithienyl‐5‐yl) are reported. The trueM¯ns for the polyphosphonates range from 1.1 to 4.6 × 104 Da and are significantly higher than those previously reported for polyphosphonates synthesized via polycondensation reactions. Thermal characterization indicates that all of the polymers are in the rubbery state at room temperature and have thermal stabilities as high as 290 °C. The linear absorption spectra, emission spectra, and emission quantum yields of the 2,2′‐bithenyl‐5‐yl substituted polyphosphonates show distinct trends with respect to the chalcogen attached to the phosphorus. Solutions of these polymers show emission at wavelengths ranging from 380 to 400 nm and, depending on the choice of X, the quantum yields are considerably larger than that of 2,2′‐bithiophene. Nonlinear optical measurements of the polyphosphonates with 2,2′‐bithenyl‐5‐yl substituents show that nonlinear absorbance increases with increasing molecular weight of X. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3663–3674

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Section: Resultsmentioning

confidence: 99%

Synthesis, thermal analysis, and linear and nonlinear optical characterization of substituted polyphosphonates derived from 1,12-dodecanediol

Freeman

Martin

Totsch

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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“…There has been a significant amount of research on materials with large third-order nonlinear optical absorptions (NLAs) due to their potential applications in optical computing [1][2][3] and optical power limiting (OPL) for eye and optical sensor protection. [4][5][6][7][8] Interest in OPL materials has increased in recent years due to the availability of low cost, high power wavelength-tunable lasers that could potentially be used to damage human eyes or optical sensors and for which fixed frequency notch filters are ineffective. 9 There have been many organic conjugated materials developed whose solutions show thirdorder NLA in red, near-infrared [10][11][12][13] and green spectral regions, [14][15][16][17] however few have been developed for the violetblue spectral region.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, linear and nonlinear optical properties of phosphonato-substituted bithiophenes derived from 2,2′-biphenol

et al. 2013

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Two new series of phosphonato-substituted bithiophenes, BpP(X)(C4H2S)2H and BpP(X)(C4H2S)2P(X)Bp (Bp = 2,2'-C12H8O2, X = O, S, Se), have been synthesized and characterized using linear absorption and emission spectra, and third-order nonlinear absorption measurements at 430 nm with 27 ps laser pulses. The compounds were synthesized in three steps: (1) reacting lithiated bithiophene with (Et2N)2PCl; (2) reacting the product from the first step with biphenol; and (3) reacting the product from the second step with the appropriate chalcogen. The X-ray crystal structures of two of the compounds, BpP(O)(C4H2S)2P(O)Bp and BpP(Se)(C4H2S)2P(Se)Bp, are reported and show a number of intermolecular π-π interactions. The linear absorption spectra, emission spectra, and emission quantum yields show distinct trends with respect to the chalcogen and the number of phosphorus substituents attached to the 2,2'-bithiophene ring. The compounds show emission maxima at wavelengths ranging from 380-400 nm and, BpP(S)(C4H2S)2H shows a 23-fold increase in fluorescence quantum yield relative to that of 2,2'-bithiophene. Fluorescence lifetimes and radiative and non-radiative decay rate constants for the first singlet excited state have been extracted from the quantum yields using time-dependent DFT calculations. Nonlinear transmission measurements indicate that all of the compounds show nonlinear absorption at 430 nm with 27 ps laser pulses in spite of their low solubilities. Notably, the nonlinear absorption threshold of a 0.16 mol L(-1) CH2Cl2 solution of BpP(Se)(C4H2S)2H is 0.9 J cm(-2). The excellent emission quantum yields and good nonlinear absorptions make these compounds promising candidates for optical power limiting applications and as host materials for violet-blue organic light emitting diodes.

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“…This suggests that the nonlinear absorption in Figure is caused by excited-state absorption (rather than two-photon absorption), since some ground-state absorption is required for excited-state absorption to take effect. Excited-state absorption has been studied in porphyrins, expanded porphyrins, ,, and phthalocyanines, − but to our knowledge this is the first observation of nonlinear absorption of this type in polythiophene complexes.…”

Section: Resultsmentioning

confidence: 97%

“…Optical Characterization of the Ligands and Complexes. The linear and nonlinear optical properties of the complexes in solution were characterized by UV−visible absorption, nonlinear absorption, − and Z-scan measurements . Together, this series of measurements allowed both the absorptive and refractive components of the optical nonlinearities of the complexes and the linear optical properties to be probed.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Characterization of Transition Metal Systems Containing Phosphino-Oligothiophene Ligands for Nonlinear Optical Materials

Myrex¹,

Gray²,

Spivey³

et al. 2006

Organometallics

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Polythiophenes exhibit interesting third-order nonlinear optical properties but poor solubilities. Incorporating polythiophenes into transition metal complexes should yield readily soluble materials, and the transition metal substituent may alter third-order nonlinear optical properties of the polythiophene. In this paper, we report the synthesis and characterization of 2-diphenylphosphinothianaphthene, A, and its trans-PdCl 2 L 2 , B, and cis-PtCl 2 L 2 , C, analogues. Additionally 2-diphenylphoshino-5:2′,5′:2′′-terthiophene, D, its trans-PdCl 2 L 2 complex, E, both first prepared by Wolf, 25 the previously unprepared cis-PtCl 2 L 2 analogue, F, and the oxide of A, G, were prepared and investigated for nonlinear optical (NLO) behavior. No appreciable third-order NLO behavior was observed for A, D, or G. However both E and F exhibited nonlinear refraction, as shown by Z-scan measurements, and nonlinear absorption. The nonlinear absorption was significantly stronger for E, indicating that the metal center has a significant affect on nonlinear absorption. This is the first reported observation of this type of nonlinear behavior in metalphosphinothiophene systems.

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Higher-order triplet interaction in energy-level modeling of excited-state absorption for an expanded porphyrin cadmium complex

Cited by 14 publications

References 24 publications

Synthesis, thermal analysis, and linear and nonlinear optical characterization of substituted polyphosphonates derived from 1,12-dodecanediol

Synthesis, thermal analysis, and linear and nonlinear optical characterization of substituted polyphosphonates derived from 1,12-dodecanediol

Synthesis, linear and nonlinear optical properties of phosphonato-substituted bithiophenes derived from 2,2′-biphenol

Synthesis and Characterization of Transition Metal Systems Containing Phosphino-Oligothiophene Ligands for Nonlinear Optical Materials

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