Electronic Modulation of Hyperpolarizable (Porphinato)zinc(II) Chromophores Featuring Ethynylphenyl-, Ethynylthiophenyl-, Ethynylthiazolyl-, and Ethynylbenzothiazolyl-Based Electron-Donating and -Accepting Moieties

Zhang, Tian-Gao; Zhao, Yuxia; Song, Kai; Asselberghs, Inge; Persoons, André; Clays, Koen; Therien, Michael J.

doi:10.1021/ic060898e

Cited by 36 publications

(45 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

“…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. 13,14,17,25,29,30,32,33,36 In this paper, we examine theoretically porphyrin-based NLO chromophores based on established D-PZn-A and Ru-PZn (ruthenium(II)[5-(4′-ethynyl-(2,2′;6′,2″-terpyridinyl))-10,20-bis(2′,6′-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc-(II)-(2,2′;6′,2″-terpyridine) 2+ ) motifs incorporating bridges that introduce proquinoidal character into the D−A conjugation pathway.…”

Section: ■ Introductionmentioning

confidence: 99%

“…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. 13,14,17,25,29,30,32,33,36 In this paper, we examine theoretically porphyrin-based NLO chromophores based on established D-PZn-A and Ru-PZn (ruthenium(II)[5-(4′-ethynyl-(2,2′;6′,2″-terpyridinyl))-10,20-bis(2′,6′-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc-(II)-(2,2′;6′,2″-terpyridine) 2+ ) motifs incorporating bridges that introduce proquinoidal character into the D−A conjugation pathway. 72,77−83 Our aim is to accomplish the meaningful theoretical design of NLO chromophores with enhanced hyperpolarizabilities, beyond those delineated thus far in benchmark D-PZn-A and Ru-PZn structures; we present a theoretical investigation of the electronic structure and NLO properties of proquinoidal variants of these chromophores in which 4,7-diethynylbenzo[c] [1,2,5]thiadiazole (E-BTD-E), 84−87 6,13-diethynylpentacene (E-PC-E), 88,89 and 9-diethynyl-6,7-dimethyl- [1,2,5]thiadiazolo [3,4-g]quinoxaline (E-TDQ-E) 72 units define a portion of the conjugated bridge connecting donor to acceptor.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Design of Coupled Porphyrin Chromophores with Unusually Large Hyperpolarizabilities

Jiang¹,

Zuber²,

Keinan³

et al. 2012

J. Phys. Chem. C

Self Cite

View full text Add to dashboard Cite

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-...

show abstract

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Design of Coupled Porphyrin Chromophores with Unusually Large Hyperpolarizabilities

Jiang¹,

Zuber²,

Keinan³

et al. 2012

J. Phys. Chem. C

Self Cite

View full text Add to dashboard Cite

show abstract

“…We have also combined our expertise in molecular nonlinear optics of organic chromophores in the field of porphyrin dyes as molecular scaffold 8,9 with that in the field of N-alkyl pyridinium acceptors 10 to engineer a new amphiphilic porphyrin dye 1 which exhibits a strong SHG signal in lipid membranes. Previous work has shown that related donoracceptor meso-ethynyl porphyrins exhibit strong second-order NLO activity.…”

Section: Introductionmentioning

confidence: 99%

“…Previous work has shown that related donoracceptor meso-ethynyl porphyrins exhibit strong second-order NLO activity. 8,9 We have modified the structure of these dyes by using polar pyridinium electron-acceptors, 10 and by omitting the orthogonal meso-aryl substituents, to create a molecule with high affinity for biological membranes. Our SHG dye can be viewed as a hybrid between donor-acceptor porphyrins and commercially available membrane-binding dyes, which can be used to probe potential changes via SHG despite their weak NLO activity.…”

Section: Introductionmentioning

confidence: 99%

Nano-engineering of materials for nonlinear optical imaging

2009

Self Cite

View full text Add to dashboard Cite

We discuss the use of genetically modified fluorescent proteins (FPs) and a specially engineered chromophore for nonlinear optical imaging. While it is clear that FPs can be used for two-photon fluorescence (TPF) microscopy, we show that they also exhibit a large second-order nonlinear optical response, useful for second-harmonic generation (SHG) imaging. The relation between the linear and nonlinear optical properties in a small series of FPs will be discussed. We also present a new optimized chromophore for combined TPF and SHG microscopy and we show imaging results obtained on this chromophore on a water droplet model system.

show abstract

Outstanding Quadratic to Septic Optical Nonlinearity at Dipolar Alkynylmetal‐Porphyrin Hybrids

et al. 2023

Self Cite

View full text Add to dashboard Cite

Porphyrins are important macrocycles with applications in several areas including therapy, catalysis, and sensing. Strong nonlinear optical (NLO) responses are the key to fully exploiting the potential of these biocompatible molecules. We herein report that certain metal-alkynyl donor/nitro acceptor-functionalized porphyrins are attractive candidates for NLO applications. We show that specific examples exhibit record quadratic optical nonlinearity, exceptional two-photon absorption, and outstanding three-photon absorption, and we report the first porphyrins that exhibit four-photon absorption. The two-, three-, and four-photon absorption maxima are found at the corresponding multiples of linear absorption bands that time-dependent density functional theory assigns as admixtures of porphyrin-localized π* ! π and donor-porphyrin to porphyrin-acceptor charge-transfer transitions.

show abstract

Electronic Modulation of Hyperpolarizable (Porphinato)zinc(II) Chromophores Featuring Ethynylphenyl-, Ethynylthiophenyl-, Ethynylthiazolyl-, and Ethynylbenzothiazolyl-Based Electron-Donating and -Accepting Moieties

Cited by 36 publications

References 73 publications

Design of Coupled Porphyrin Chromophores with Unusually Large Hyperpolarizabilities

Design of Coupled Porphyrin Chromophores with Unusually Large Hyperpolarizabilities

Nano-engineering of materials for nonlinear optical imaging

Outstanding Quadratic to Septic Optical Nonlinearity at Dipolar Alkynylmetal‐Porphyrin Hybrids

Contact Info

Product

Resources

About