1,3,5-Tricyano-2,4,6-tris(vinyl)benzene Derivatives with Large Second-Order Nonlinear Optical Properties

Cho, Bong Rae; Park, Soon Bong; Lee, Seung-Jae; Son, Kyung Hwa; Lee, Sang Hae; Lee, Myungja; Yoo, Jun; Lee, Yun Kyong; Lee, Geon Joon; Kang, T. I.; Cho, Minhaeng; Jeon, Sanggeun

doi:10.1021/ja0025595

Cited by 77 publications

(49 citation statements)

References 21 publications

(28 reference statements)

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“…While wavelengths near 1500 nm define a critically important telecommunications spectral region, no molecular chromophore has thus far been delineated that exhibits a dynamic hyperpolarizability measured at a 1.5 μm incident irradiation wavelength that exceeds 700 × 10 –30 esu; 27,61,65,74−81 this work provides new insights into the design of octopolar NLO chromophores, and demonstrates the utility of MPZnM compositions for realizing substantial β HRS values at long wavelengths.…”

Section: Introductionmentioning

confidence: 80%

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores

et al. 2016

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Octopolar D2-symmetric chromophores, based on the MPZnM supermolecular motif in which (porphinato)zinc(II) (PZn) and ruthenium(II) polypyridyl (M) structural units are connected via ethyne linkages, were synthesized. These structures take advantage of electron-rich meso-arylporphyrin or electron-poor meso-(perfluoroalkyl)porphyrin macrocycles, unsubstituted terpyridyl and 4′-pyrrolidinyl-2,2′;6′,2″-terpyridyl ligands, and modulation of metal(II) polypyridyl-to-(porphinato)zinc connectivity, to probe how electronic and geometric factors impact the measured hyperpolarizability. Transient absorption spectra obtained at early time delays (tdelay < 400 fs) demonstrate fast excited-state relaxation, and formation of a highly polarized T1 excited state; the T1 states of these chromophores display expansive, intense T1 → Tn absorption manifolds that dominate the 800–1200 nm region of the NIR, long (μs) triplet-state lifetimes, and unusually large NIR excited absorptive extinction coefficients [ε(T1 → Tn) ∼ 105 M–1 cm–1]. Dynamic hyperpolarizability (βλ) values were determined from hyper-Rayleigh light scattering (HRS) measurements, carried out at multiple incident irradiation wavelengths spanning the 800–1500 nm spectral domain. The measured βHRS value (4600 ± 1200 × 10–30 esu) for one of these complexes, RuPZnRu, is the largest yet reported for any chromophore at a 1500 nm irradiation wavelength, highlighting that appropriate engineering of strong electronic coupling between multiple charge-transfer oscillators provides a critical design strategy to realize octopolar NLO chromophores exhibiting large βHRS values at telecom-relevant wavelengths. Generalized Thomas–Kuhn sum (TKS) rules were utilized to compute the effective excited-state-to-excited-state transition dipole moments from experimental linear-absorption spectra; these data were then utilized to compute hyperpolarizabilities as a function of frequency, that include two- and three-state contributions for both βzzz and βxzx tensor components to the RuPZnRu hyperpolarizability spectrum. This analysis predicts that the βzzz and βxzx tensor contributions to the RuPZnRu hyperpolarizability spectrum maximize near 1550 nm, in agreement with experimental data. The TKS analysis suggests that relative to analogous dipolar chromophores, octopolar supermolecules will be likely characterized by more intricate dependences of the measured hyperpolarizability upon irradiation wavelength due to the interactions among multiple different β tensor components.

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Section: Introductionmentioning

confidence: 80%

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores

et al. 2016

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“…For rather pronounced efficiency, d eff = 3.09d eff (KDP), the melaminium cations may be responsible. These cations belong to so-called octupolar molecules widely described in literature [19][20][21][22][23][24][25][26][27][28][29][30].…”

Section: Discussionmentioning

confidence: 99%

Vibrational, calorimetric and nonlinear optical studies of melaminium-bis(trichloroacetate) monohydrate molecular–ionic crystal

et al. 2007

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“…Evolution of NLO octopoles from dipolar chromophoric archetypes has been demonstrated, but such examples are confined largely to proof-of-principle targets that possess only modest hyperpolarizabilities; cases in point include the syntheses of 1,3,5-tridonor-2,4,6-triaccpetor-aryl compounds inspired by the corresponding dipolar 1-donor-4-acceptor-aryl structures 68,70,72-74,76. This fact has been emphasized recently by Torres and coworkers, who has noted that virtually all NLO octopoles reported to date are in fact octopolar expansions of the dipolar paradigm 80.…”

Section: Introductionmentioning

confidence: 99%

The Roles of Molecular Structure and Effective Optical Symmetry in Evolving Dipolar Chromophoric Building Blocks to Potent Octopolar Nonlinear Optical Chromophores

et al. 2011

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A series of mono-, bis-, tris-, and tetrakis-(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes has been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4′-, and 4″-positions. These supermolecular chromophores, based on the 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+ bishexafluorophosphate (RuPZn) archetype, evince strong mixing of the PZn-based oscillator strength with ruthenium terpyridyl charge resonance bands. Potentiometric and linear absorption spectroscopic data indicate that for structures in which multiple PZn moieties are linked via ethynes to a [Ru(tpy) 2 ] 2+ core, little electronic coupling is manifest between PZn units, regardless of whether they are located on the same or opposite tpy ligand. Congruent with these experiments, pump-probe transient absorption studies suggest that the individual RuPZn fragments of these structures exhibit, at best, only modest excited-state electronic interactions that derive from factors other than the dipole-dipole interactions of these strong oscillators; this approximate independent character of the component RuPZn oscillators enables fabrication of NLO multipoles with extraordinary hyperpolarizabilities.Dynamic hyperpolarizability (β λ ) values and depolarization ratios (ρ) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (λ inc ) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (β HRS values), while evolving (PF 6 ) 2 possessing a β HRS value at 1300 nm more than a factor of three larger than that determined for any chromophore having octopolar symmetry examined to date. Because NLO octopoles possess omnidirectional NLO responses while circumventing the electrostatic interactions that drive bulk-phase centrosymmetry for NLO dipoles at high chromophore concentrations, the advent of octopolar NLO chromophores having vastly superior β HRS values at technologically important wavelengths will motivate new experimental approaches to achieve acentric order in both bulk-phase and thin film structures.

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1,3,5-Tricyano-2,4,6-tris(vinyl)benzene Derivatives with Large Second-Order Nonlinear Optical Properties

Cited by 77 publications

References 21 publications

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores

Vibrational, calorimetric and nonlinear optical studies of melaminium-bis(trichloroacetate) monohydrate molecular–ionic crystal

The Roles of Molecular Structure and Effective Optical Symmetry in Evolving Dipolar Chromophoric Building Blocks to Potent Octopolar Nonlinear Optical Chromophores

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