Phthalocyanines and related compounds as switchable materials upon strong irradiation: the molecular engineering behind the optical limiting effect

Dini, Danilo

doi:10.1016/j.ssi.2003.08.046

Cited by 49 publications

(22 citation statements)

References 33 publications

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“…The induction of electronic effects and their influence on the NLO properties is another important aspect related to the presence of peripheral substituents on phthalocyanines. The comparison of the OL behavior at 532 nm with 10 ns laser pulses for the series of compounds 674 – 677 (Chart ) proved that the species possessing electron-withdrawing groups as peripheral substituents displayed a more effective OL . In fact, compounds 675 and 676 displayed the lowest values of optical transmittance at high levels of irradiation .…”

Section: Phthalocyanines and Related Macrocyclesmentioning

confidence: 96%

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

2016

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The control of luminous radiation has extremely important implications for modern and future technologies as well as in medicine. In this Review, we detail chemical structures and their relevant photophysical features for various groups of materials, including organic dyes such as metalloporphyrins and metallophthalocyanines (and derivatives), other common organic materials, mixed metal complexes and clusters, fullerenes, dendrimeric nanocomposites, polymeric materials (organic and/or inorganic), inorganic semiconductors, and other nanoscopic materials, utilized or potentially useful for the realization of devices able to filter in a smart way an external radiation. The concept of smart is referred to the characteristic of those materials that are capable to filter the radiation in a dynamic way without the need of an ancillary system for the activation of the required transmission change. In particular, this Review gives emphasis to the nonlinear optical properties of photoactive materials for the function of optical power limiting. All known mechanisms of optical limiting have been analyzed and discussed for the different types of materials.

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Section: Phthalocyanines and Related Macrocyclesmentioning

confidence: 96%

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

2016

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“…due to novel intense and tunable light sources [2]. Organic compounds are good candidates as OL materials [3,4], and among them macrocyclic molecules are particularly effective, due to their large and delocalized π-electron network [5]. Phthalocyanines and porphyrins present several advantages in this field [6,7]: in addition to their excellent chemical processability and versatility, they are characterized by a complex spectrum in the UV -visible range, which can be tuned by chemical modifications, either by decorating the organic network or by inserting a metal atom [8][9][10].…”

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confidence: 99%

Ab InitioSimulation of Optical Limiting: The Case of Metal-Free Phthalocyanine

et al. 2014

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We present a fully ab initio, non-perturbative description of the optical limiting properties of a metal-free phthalocyanine, by simulating the effects of a broadband electric field of increasing intensity. The results confirm reverse saturable absorption as leading mechanism for optical limiting phenomena in this system and reveal that a number of dipole-forbidden excitations are populated by excited-state absorption, at more intense external fields. The excellent agreement with the experimental data supports our approach as a powerful tool to predict optical limiting, in view of applications.PACS numbers: 82.37. Vb, 71.15.Mb, 78.40.Me Optical limiting (OL), a strong attenuation of the light transmittance through a material at increasing input intensity, is a prototype nonlinear phenomenon of relevance for an entire class of devices [1]. It has received rising attention in view of the need to protect light-sensitive elements, including the human eye, from optical damage e.g. due to novel intense and tunable light sources [2]. Organic compounds are good candidates as OL materials [3,4], and among them macrocyclic molecules are particularly effective, due to their large and delocalized π-electron network [5]. Phthalocyanines and porphyrins present several advantages in this field [6,7]: in addition to their excellent chemical processability and versatility, they are characterized by a complex spectrum in the UV -visible range, which can be tuned by chemical modifications, either by decorating the organic network or by inserting a metal atom [8][9][10]. A number of experimental studies in the last decades provided a general picture of the main physical mechanisms driving optical limiting in these molecules [11][12][13]. Previous theoretical studies (see e.g. Ref.[14]), however, are mostly limited to a phenomenological level of description, and are therefore unable to clarify the microscopic origin of OL phenomena and to predict the behavior of different systems.Within the framework of real-time time-dependent density functional theory (TDDFT), we perform a fully ab initio investigation of the OL properties of a metalfree phthalocyanine. The calculated optical spectra are the key ingredient to determine the OL curve in the frequency region of interest, upon increasing irradiance. A large excited-state absorption around the green visible region emerges as the driving mechanism for reverse saturable absorption (RSA) and hence for OL effects in these systems. Our results reproduce the nonlinear behavior of the intensity-dependent absorption coefficient, which is a fingerprint of optical limiting, and confirms the validity of our approach to characterize the response of macromolecules to strong electromagnetic fields. The insight 2 ), in agreement with the experimental spectrum (dashed line, from Ref. [7]). The visible (∼ 2 eV, Qband) and the near UV region (∼ 3-4 eV, B-band) are separated by a large absorption valley (2.3 -2.9 eV, OL).into the microscopic origin of these phenomena, provided by ab initio calculation...

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Several groups have argued about nuances of these materials in extensive range of photonic applications. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Our comprehensive experiments and detailed modeling, along with the obtained nonlinear coefficients, strongly suggest that these molecules are potential molecules with large nonlinear coefficients in ns, ps, and fs time domains with ultrafast response times. More so, phthalocyanines and their derivatives possess attractive third-order nonlinearities and figures of merit with outstanding applications in optical limiting and ultrafast all-optical switching.…”

Section: Introductionmentioning

confidence: 83%

Picosecond and nanosecond third order nonlinear optical characterization of Cu and Ni phthalocyanines using Z-scan technique

Rao

Prasad

Giribabu

et al. 2010

Organic Photonic Materials and Devices XII

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Herein we present our results from the picosecond and nanosecond nonlinear optical studies of two novel phthalocyanines {[(SO 3 Na) 4 CuPc] and [(SO 3 Na) 4 NiPc]} using the Z-scan technique. Open aperture Z-scan data revealed that the picosecond nonlinear absorption was dominated by three-photon absorption while in the nanosecond domain reverse saturable absorption prevailed. Closed aperture data with nanosecond pulses indicated strong thermal, negative nonlinearity while picosecond excitation demonstrated positive nonlinearity. The nonlinearity in CuPc was higher than in NiPc in both the time domains. The nonlinear coefficients extracted from the fits to experimental data were large compared to some of the recently reported works on similar molecules.

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Phthalocyanines and related compounds as switchable materials upon strong irradiation: the molecular engineering behind the optical limiting effect

Cited by 49 publications

References 33 publications

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

Ab InitioSimulation of Optical Limiting: The Case of Metal-Free Phthalocyanine

Picosecond and nanosecond third order nonlinear optical characterization of Cu and Ni phthalocyanines using Z-scan technique

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