Amphiphilic Porphyrins for Second Harmonic Generation Imaging

Reeve, James E.; Collins, Hugh; Mey, Kurt De; Köhl, Michael; Thorley, Karl J.; Paulsen, Ole; Clays, Koen; Anderson, Harry L.

doi:10.1021/ja8061369

Cited by 136 publications

(137 citation statements)

References 22 publications

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“…[1][2][3][4][5][6][7][8][9][10][11][12] The aggregation and selfassembly of porphyrins are an area of intense research, and so far, many porphyrin supramolecular assemblies, which can be used as molecular-level electronics, sensors, photonic materials, and for molecular recognition, have been prepared through noncovalent interactions such as π-π stacking interactions and hydrogen-bonding interactions. [13][14][15][16][17][18][19][20][21][22][23][24] The coordination of metal ions at the center of the porphyrin ring, as well as the substitution at the periphery of the porphyrin rings by suitable organic groups, provide various programming elements for the design of porphyrin supramolecular assemblies.…”

Section: Introductionmentioning

confidence: 99%

Change in Supramolecular Networks through In Situ Esterification of Porphyrins

Chen

Fukuzumi

2009

Eur J Inorg Chem

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(5), and Co (6); Me = CH 3 ], and two nonmetalated compounds, TCPP-Et 4 (7) and TCPP-Me 4 ·H 2 O (8), were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction. Compounds 1-3 feature an isolated structure with a planar macrocycle and an embedded metal-ion coordinating to four pyrrole nitrogen atoms. Compound 4 is characterized as a two-dimensional coordination polymer, and the zinc ion coordinates to four nitrogen atoms and two oxygen atoms. Compound 4 possesses a large void space (361 Å 3 ), which corresponds to 14 % of the unit-cell volume. Compounds 5 and 6 are characteristic of an isolated motif with a four-coordinate metal ion and a saddle-distorted nonplanar porphyrin macrocycle. Nonmetalated compounds 7 and 8 also show an

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Section: Introductionmentioning

confidence: 99%

Change in Supramolecular Networks through In Situ Esterification of Porphyrins

Chen

Fukuzumi

2009

Eur J Inorg Chem

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“…Elongation of the conjugated π-system results in considerable red-shifts in both the Soret and Q-band spectral regions [1−3] and enhanced substituent effects of appended functional groups [4−6]. Owing to their unique optical properties, arylethynyl porphyrins are used in a wide range of applications including artificial photosynthetic systems [7−10], dye-sensitized and organic solar cells [11−17], nonlinear optical materials [18−22], and biological imaging [23].…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic characterization of free-base hydroxy(arylethynyl)porphyrins in acidic and basic media

Evens

Splan

2017

J. Porphyrins Phthalocyanines

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ABSTRACT:The addition of arylethynyl groups to the porphyrin macrocycle represents an effective strategy with which to enhance the light-harvesting properties of porphyrins. We now extend this modification to arylethynyl porphyrins with two or four p-hydroxyphenyl substituents. Arylethynyl porphyrins bearing four, but not two, p-hydroxyphenyl substituents show evidence of aggregation under acidic conditions. Under basic conditions, deprotonation of the peripheral hydroxyphenyl substituents results in substantially red-shifted spectral features and enhanced absorption in the Q-band region. When the hydroxyphenyl groups are appended to the porphyrin macrocylce via the ethynyl spacers, the spectral shifts observed upon deprotonation are significantly enhanced relative to those observed for hydroxyphenylporphyrins, highlighting the role of expanded conjugation in altering porphyrin photophysics.

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“…12−14,17,18,25,26,29−36,55−62 Porphyrins and their corresponding ethynylated and ethyne-linked derivatives are attractive building blocks for such materials because of their extended electronic delocalization, large oscillator strengths, and substantial polarizabilities; 12−14,38,61,63−76 in addition to providing for substantial β λ values, such porphyrin-based donorbridge-acceptor systems manifest excellent thermal stabilities. 13,17,25,29,30,32,34,61 Benchmark examples of these robust structures that possess high β λ values include [5-((4′-(dimethylamino)phenyl)ethynyl)-15-((4″-nitrophenyl)-ethynyl)-10,20-diphenylporphinato]zinc(II) (D-PZn-A) 13,14,17 and closely related structures, 29,30,34 as well as chromophores where (porphinato)zinc(II) (PZn) and metal(II)polypyridyl (M) units are linked via an ethyne bridge (M-PZn species). 25,26,[29][30][31][32][33]36,57 The hyperpolarizabilities of these systems display complex irradiation wavelength dependences; measured values of β λ for these structures are as high as several thousand ×10 −30 esu.…”

Section: ■ Introductionmentioning

confidence: 99%

Design of Coupled Porphyrin Chromophores with Unusually Large Hyperpolarizabilities

Jiang¹,

Zuber²,

Keinan³

et al. 2012

J. Phys. Chem. C

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A new series of push−pull porphyrin-based chromophores with unusually large static first hyperpolarizabilities are designed on the basis of coupled-perturbed Hartree−Fock and density functional calculations. The proper combination of critical building blocks, including a ruthenium(II) bisterpyridine complex, proquinoidal thiadiazoloquinoxaline, and (porphinato)zinc(II) units, gives rise to considerable predicted enhancements of the static nonlinear optical (NLO) response, computed to be as large as 11 300 × 10 −30 esu, 2 orders of magnitude larger than the benchmark [5-((4′-(dimethylamino)phenyl)ethynyl)-15-((4″-nitrophenyl)ethynyl)porphinato]zinc(II) chromophore. A two-state model was found to be useful for the qualitative description of the first hyperpolarizabilities in this class of NLO chromophores, which are predicted to have hyperpolarizabilities approaching the fundamental limit predicted to be attainable by empirical theoretical models. ■ INTRODUCTIONNonlinear optical (NLO) materials have attracted considerable attention due to potential applications in optics and optoelectronics that include information storage, image processing, frequency conversion, optical signal processing, optical computing, and dynamic imaging. 1−3 Inorganic crystals such as LiNbO 3 and KTiOPO 4 have been widely used in commercial NLO devices. 2 Since the 1990s, however, a large number of organic compounds with extended conjugation have emerged as candidates for electrooptically functional elements in NLO materials. 1,4−40 The advantages of organic materials over traditional inorganic crystals stem from their lower dielectric constants, potentially faster and larger NLO responses, and ease of processing; furthermore, the considerable topological and electronic structural diversity made available through chemical synthesis offers the opportunity for application-specific chromophore optimization. With respect to organic NLO materials, the donor-bridge (π-electron system)-acceptor or push−pull structure, has served as a classic design motif. 2,4−7,9−36,38−40 Although many theoretical 41−52 and experimental groups have been working for decades on the design of new structures with large second order NLO properties, relatively few examples of chromophores have been delineated that possess β λ values (dynamic hyperpolarizabilities) that exceed 1000 × 10 − 3 0 esu at telecommunications-relevant wavelengths. 9,13,14,17,24,25,[28][29][30]33,37,53,54 Due in part to the fact that a large fraction of these highly hyperpolarizable chromophores exploits a porphyrinic component, there has been increased i n t e r e s t i n p o r p h y r i n -b a s e d N L O m a t e r ials. 12−14,17,18,25,26,29−36,55−62 Porphyrins and their corresponding ethynylated and ethyne-linked derivatives are attractive building blocks for such materials because of their extended electronic delocalization, large oscillator strengths, and substantial polarizabilities; 12−14,38,61,63−76 in addition to providing for substantial β λ values, such porphyrin-based donorbridge-...

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Amphiphilic Porphyrins for Second Harmonic Generation Imaging

Cited by 136 publications

References 22 publications

Change in Supramolecular Networks through In Situ Esterification of Porphyrins

Change in Supramolecular Networks through In Situ Esterification of Porphyrins

Spectroscopic characterization of free-base hydroxy(arylethynyl)porphyrins in acidic and basic media

Design of Coupled Porphyrin Chromophores with Unusually Large Hyperpolarizabilities

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