ChemInform Abstract: A Straightforward Modular Approach to NLO‐Active β‐Amino Vinyl Nitrothiophenes

Abstract

A Straightforward Modular Approach to NLO-Active β-Amino Vinyl Nitrothiophenes-[with significant first hyperpolarizabilities and interesting morphological stability].-(MUELLER, THOMAS J. J.; ROBERT, JAN P.; SCHMAEZLIN, ELMAR; BRAEUCHLE, CHRISTOPH;

Design, Synthesis, Linear, and Nonlinear Optical Properties of Conjugated (Porphinato)zinc(II)-Based Donor−Acceptor Chromophores Featuring Nitrothiophenyl and Nitrooligothiophenyl Electron-Accepting Moieties

“…Oligothiophenes bearing electron-releasing or -accepting groups 35,56 have featured in structures that probe intramolecular electronic and energy transfer reactions 44,46 as well as an extensive family of hyperpolarizable chromophores. 16,[22][23][24][25][26][27][28][29][30][31][32][33][34] Studies that examined the impact of terminal oligothiophene substituents on electrochemical and optical properties 35 demonstrate that nitro functionality drives bathochromic shifts of the S 0 f S n electronic transitions, large emission band Stokes shifts, and substantial solvatochromism. While these terminally nitro-substituted oligothiophenes have previously been synthesized and examined mainly for their potential utility as phototoxic agents, [57][58][59][60][61] their electronic structural properties suggest that such conjugated oligothiophenes may find utility in driving preferential excitedstate electronic redistributions within a hyperpolarizable pushpull ethynylporphyrin structural motif.…”

“…The thiophene-based organic reagents 2-bromo-5-nitrothiophene, 2-iodothiophene, thiophene, and 2,2′-bithiophene were purchased from Aldrich, while 2-ethynyl-5-nitrothiophene was synthesized via established methods. 23,36,37 5,15-Bis[3,5-di-(3,3-dimethyl-1-butyloxy)phenyl]porphyrin, 3 [5-bromo-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) 3 (porphyrin 1), [5,15-dibromo-10,20-bis(3,5-bis(3,3dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) 3,38 (porphyrin 2), [5-(4′dimethylaminophenylethynyl)-15-bromo-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) 11 (porphyrin 4), and [5-(4′,4′,5′,5′tetramethyl[1′,3′,2′]dioxaborolan-2′-yl)-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) 39 (porphyrin 5) were prepared using methods similar to that reported previously. 1 H NMR spectra were recorded on either a Bru ¨ker AC-250 or Bru ¨ker AM-360 spectrometer.…”

“…Similarly, owing to the low resonance energy of the thiophene heterocycle, [13][14][15][16][17][18][19] thiophenes have found utility in a wide range of nonlinear optical (NLO) materials. 16,[20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] Germane to this latter work are recent studies that examine the impact of terminal oligothiophene substituents on electrochemical and optical properties 35 and demonstrate that oligothiophene photophysical properties are particularly sensitive to substituent effects; for example, it has been established that the nitro functionality drives bathochromic shifts of the S 0 f S n electronic transitions, large emission band Stokes shifts, and substantial solvatochromism. These established electrooptic properties suggest that such conjugated oligothiophenes may be effective in driving preferential excited-state electronic redistributions when used in combination with hyperpolarizable push-pull ethynylporphyrin structures.…”

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

“…2-Ethynyl-5-nitrothiophene was synthesized via established methods. [34][35][36] 5-(Trimethylsilylethynyl)-thiophene-2-carbaldehyde was synthesized following a literature method. 37 The syntheses of 5,15-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphyrin, [5- phyrin 3), and [5-ethynyl-15-(4-nitrophenylethynyl)-10,20-diarylporphinato]zinc(II) (porphyrin 4) have been reported previously.…”