Synthesis, Characterization, and Nonlinear Optical Study of Metalloporphyrins

McEwan, Ken; Lewis, Keith L.; Guo, Yanyan; Chng, Leng Leng; Lee, Y.-W.; Lau, W.-P.; Lai, Kin Seng

doi:10.1002/adfm.200304288

Cited by 86 publications

(48 citation statements)

References 18 publications

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“…McEwan et al reported a similar trend to that found for compounds 12, 13 and 14 [4]. The authors investigated the effect of different functional groups at the para position of the meso phenyl ring in tetrasubstituted porphyrins on their optical limiting efficiency.…”

Section: Monomerssupporting

confidence: 54%

“…This might be due to the presence of the closed shell metal zinc in the central cavity which renders this compound more promising in comparison to others of similar structure. Closed shell metals were reported to have favourable effect on the NLA as they produce an increase in the intersystem crossing rate resulting in higher quantum yield for the triplet state [3][4][5]10]. Reports indicate brominated porphyrins as very promising materials for optical limiting applications [24,25].…”

Section: Monomersmentioning

confidence: 99%

“…One of those applications requires broadband passive optical limiters which are of fundamental significance in the protection of sensitive optical elements and human eyes against damage on the accidental exposure to laser light. Strong nonlinear absorption (NLA) over a broad range of the visible spectrum along with long lived excited state lifetimes coupled with good thermal-and photostability renders porphyrins as promising candidates for effective optical limiting materials [3][4][5]. Moreover, the design potential of these materials offers a unique opportunity for fine tuning the linear and NLO properties and thus of the optical limiting efficiency of porphyrin based compounds [6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

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Correlation studies on structurally diverse porphyrin monomers, dimers and trimers and their nonlinear optical responses

Zawadzka

Wang

Blau

et al. 2009

Chemical Physics Letters

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GRAPHICAL ABSTRACT Pictogram SynopsisThe nonlinear optical absorption of porphyrins can be modulated via chemical modifications of the ring system and the regiochemical arrangement of the substituents. ACCEPTED MANUSCRIPT ABSTRACTAn investigation of the nonlinear absorption of a wide range of structurally diverse porphyrin monomers, bisporphyrins and trisporphyrins, using open Z-scan technique with 6 ns pulsed laser operating at 532 nm was carried out. Using the theory of reverse saturable absorption, the intensity dependent nonlinear absorption coefficient eff was deduced from the experiments. Monomers which Soret band maximum was situated closer to the experimental wavelength had higher eff . The eff of dimers and trimers were in the same range as for monomers. The highest eff = 5.3 10 -8 cmW -1 was found for a zinc complex of 5,15-A 2 B 2 type porphyrins with 3-methoxyphenyl and trimethylsilyl-ethynyl groups in the meso positions.

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Section: Monomerssupporting

confidence: 54%

Section: Monomersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Correlation studies on structurally diverse porphyrin monomers, dimers and trimers and their nonlinear optical responses

Zawadzka

Wang

Blau

et al. 2009

Chemical Physics Letters

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“…Currently, optical power limiting (OPL) materials in use are largely small molecules such as fullerenes (e.g., C 60 ), [8,9] phthalocyanines (Pc), [10][11][12] porphyrins, [13,14] diacetylenes, [15] nanotubes, [16] and metal-organic compounds, [17][18][19][20] due to their fast response speed (picoseconds) and large optical nonlinearities. [7] Together with C 60 and its derivatives, metallophthalocyanines and metalloporphyrins are amongst the most effective OPL materials, in which the heavy-metal effect facilitates the spin-orbit coupling (SOC) and significantly magnifies the OPL response by enhancement of the intersystem crossing (ISC) from the first singlet state (S 1 ) to the first triplet state (T 1 ), thereby giving a good access to the highly absorbing triplet-state manifold.…”

Section: Introductionmentioning

confidence: 99%

Symmetric Versus Unsymmetric Platinum(II) Bis(aryleneethynylene)s with Distinct Electronic Structures for Optical Power Limiting/Optical Transparency Trade‐off Optimization

Zhou

Wong

Poon

et al. 2009

Adv Funct Materials

134

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A new series of symmetric and unsymmetric Pt(II) bis(acetylide) complexes of the type DC≡CPt(PBu3)2C≡CD (DPtD), AC≡CPt(PBu3)2C≡CA (APtA) and DC≡CPt(PBu3)2C≡CA (DPtA) (D, donor groups; A, acceptor groups) are synthesized, and show superior optical power limiting (OPL)/optical transparency trade‐offs. By tailoring the electronic properties of the aryleneethynylene group, distinct electronic structures for these metalated complexes can be obtained, which significantly affect their photophysical behavior and OPL properties for a nanosecond laser pulse at 532 nm. Electronic influence of the ligand type and the molecular symmetry of metal group on the optical transparency/nonlinearity optimization is thoroughly elucidated. Generally, aryleneethynylene ligands with π electron‐accepting nature will effectively enhance the harvesting efficiency of the triplet excited states. The ligand variation to the OPL strength of these Pt(II) compounds follows the order: DPtD > DPtA > APtA. These results could be attributed to the distinctive excited state character induced by their different electronic structures, on the basis of the data from both photophysical studies and theoretical calculations. All of the complexes show very good optical transparencies in the visible‐light region and exhibit excellent OPL responses with very impressive figure of merit σex/σo values (up to 17), which remarkably outweigh those of state‐of‐the‐art reverse saturable absorption dyes such as C60 and metallophthalocyanines with very poor transparencies. Their lower optical‐limiting thresholds (0.05 J cm−2 at 92% linear transmittance) compared with that of the best materials (ca. 0.07 J cm−2 for InPc and PbPc dyes) currently in use will render these highly transparent materials promising candidates for practical OPL devices for the protection of human eyes and other delicate electro‐optic sensors.

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“…9,20,21 Both King's complex and C-60 variants show both RSA and nonlinear scattering in solution. 9,20,21 Although these and other classes of chromophores, such as porphyrins, 15,16 show promising nonlinearities, performance is hampered by linear absorption in the visible wavelength region. [22][23][24] Pt-acetylides show good OPL response throughout the visible wavelength band while retaining low linear absorption.…”

Section: Introductionmentioning

confidence: 99%

How to assess good candidate molecules for self-activated optical power limiting

et al. 2018

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Abstract. Reverse saturable absorbers have shown great potential to attenuate laser radiation. Good candidate molecules and various particles have successfully been incorporated into different glass matrices, enabling the creation of self-activated filters against damaging laser radiation. Although the performance of such filters has been impressive, work is still ongoing to improve the performance in a wider range of wavelengths and pulse widths. The purpose of this tutorial is, from an optical engineering perspective, to give an understanding of the strengths and weaknesses of this class of smart materials, how relevant photophysical parameters are measured and influence system performance and comment on the pitfalls in experimental evaluation of materials. A numerical population model in combination with simple physical formulas is used to demonstrate system behavior from a performance standpoint. Geometrical reasoning shows the advantage of reverse saturable absorption over nonlinear scattering due to a fraction of scattered light being recollected by imaging system optics. The numerical population model illustrates the importance of the optical power limiting performance during the leading edge of a nanosecond pulse, which is most strongly influenced by changes in the two-photon absorption cross section and the triplet linear absorption cross section for a modeled Pt-acetylide. This tutorial not only targets optical engineers evaluating reverse saturable absorbing materials but also aims to assist researchers with a chemistry background working on optical power limiting materials. We also present photophysical data for a series of coumarins that can be useful for the determination of quantum yields and two-photon cross sections and show examples of characterization of molecules with excited triplet states.

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Synthesis, Characterization, and Nonlinear Optical Study of Metalloporphyrins

Cited by 86 publications

References 18 publications

Correlation studies on structurally diverse porphyrin monomers, dimers and trimers and their nonlinear optical responses

Correlation studies on structurally diverse porphyrin monomers, dimers and trimers and their nonlinear optical responses

Symmetric Versus Unsymmetric Platinum(II) Bis(aryleneethynylene)s with Distinct Electronic Structures for Optical Power Limiting/Optical Transparency Trade‐off Optimization

How to assess good candidate molecules for self-activated optical power limiting

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