Synthesis, optical and structural properties of sanidic liquid crystal (cholesteryl)benzoate-ethynylene oligomers and polymer

Castruita, Griselda; García, Vladimir; Arias, Eduardo; Moggio, Ivana; Ziolo, Ronald F.; Ponce, Arturo; González, Virgilio Ángel González; Haley, Joy E.; Flikkema, Jonathan L.; Cooper, Thomas M.

doi:10.1039/c2jm14918d

Cited by 20 publications

(19 citation statements)

References 40 publications

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“…The amine of 7 is used to form an intermediary diazonium salt, which is obtained in 90 %y ield by am odification of the Schiemann reaction. [26] Diazonium cation 8 is stable and can be isolated through suction filtration.A fter its dissolution in a mixture of cold DMF and diethylamine, triazene 9 is obtained in 68 %y ield. Then, TMSA is Pd/Cu cross-coupledt o9 in triethylamine.…”

Section: Resultsmentioning

confidence: 99%

Dual Emission of meso‐Phenyleneethynylene–BODIPY Oligomers: Synthesis, Photophysics, and Theoretical Optoelectronic Study

Flores

León

Turlakov

et al. 2020

Chemistry A European J

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Two series of 2,5‐di(butoxy)phenyleneethynylenes, one halogenated (nPEC4‐X; n=2, 3, or 4) and the other boron‐dipyrromethene (BODIPY) terminated (nPEC4‐By; n=3, 4, or 5; By=BODIPY), were synthesized monodirectionally by the step‐by‐step approach and the molecular structure was corroborated by NMR spectroscopy (1H, 13C‐DEPTQ‐135, COSY, HSQC, HMBC, 11B, 19F) and MALDI‐TOF mass spectrometry. The multiplicity and J‐coupling constants of 1H, 11B, and 19F/11B NMR signals revealed, in the nPEC4‐By series, that the phenyl in the meso position of BODIPY becomes electronically part of the conjugation of the phenyleneethynylene chain, whereas BODIPY is electronically isolated. The photophysical, electrochemical, and theoretical studies confirm this finding because the properties of nPEC4‐By are comparable to those of the nPEC4‐X oligomers and BODIPY, indicating negligible electron communication between BODIPY and the nPEC4 moieties. Nevertheless, energy transfer (ET) from nPEC4 to BODIPY was rationalized by spectroscopy and theoretical calculations. Its yield decreases with the nPEC4 conjugation length, according to the increase in distance between the two chromophores, resulting in dual emission for the longest oligomer in which ET is quenched.

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Section: Resultsmentioning

confidence: 99%

Dual Emission of meso‐Phenyleneethynylene–BODIPY Oligomers: Synthesis, Photophysics, and Theoretical Optoelectronic Study

Flores

León

Turlakov

et al. 2020

Chemistry A European J

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“…Successive selective deprotections that were followed by dimerization allowed for the access to oligomers with an even number of phenylene ethynylene moieties ( Scheme 1 a). The same synthetic approach was used by Moggio et al [ 7 , 8 ] for the preparation of three families of odd side-chain-substituted OPEs ( Scheme 1 b), two of which were studied as mesomorphic materials. Compound 1 in Table 1 , belonging to the most recent family of R-terminated (dodecyl)benzoateethynylene oligomers, was applied in the staining of bacteria [ 9 ].…”

Section: Synthesis Of Opesmentioning

confidence: 99%

A Portrait of the OPE as a Biological Agent

2021

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Oligophenylene ethynylenes, known as OPEs, are a sequence of aromatic rings linked by triple bonds, the properties of which can be modulated by varying the length of the rigid main chain or/and the nature and position of the substituents on the aromatic units. They are luminescent molecules with high quantum yields and can be designed to enter a cell and act as antimicrobial and antiviral compounds, as biocompatible fluorescent probes directed towards target organelles in living cells, as labelling agents, as selective sensors for the detection of fibrillar and prefibrillar amyloid in the proteic field and in a fluorescence turn-on system for the detection of saccharides, as photosensitizers in photodynamic therapy (due to their capacity to highly induce toxicity after light activation), and as drug delivery systems. The antibacterial properties of OPEs have been the most studied against very popular and resistant pathogens, and in this paper the achievements of these studies are reviewed, together with almost all the other roles held by such oligomers. In the recent decade, their antifungal and antiviral effects have attracted the attention of researchers who believe OPEs to be possible biocides of the future. The review describes, for instance, the preliminary results obtained with OPEs against severe acute respiratory syndrome coronavirus 2, the virus responsible for the COVID-19 pandemic.

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“…[ 33 ] Also Castruita et al have synthesized benzoate‐ethynylene oligomers with a cholesterol moiety and proposed their supramolecular assembly in bilayers. [ 34 ] Here, we describe the liquid crystalline behavior and spectroscopic properties of a cholesteric liquid crystal platinum acetylide PE1‐CN‐Chol. We also provide characterization and interpretation of the self‐assembly studied by scanning tunneling microscopy (STM) imaging and molecular dynamics (MD) simulations.…”

Section: Introductionmentioning

confidence: 99%

Nanoscale Organization of a Platinum(II) Acetylide Cholesteric Liquid Crystal Molecular Glass for Photonics Applications

Cooper

Haley

Long

et al. 2020

Adv Funct Materials

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The fabrication, molecular structure, and spectroscopy of a stable cholesteric liquid crystal platinum acetylide glass obtained from trans-Pt(PEt 3) 2 (CC− C 6 H 5 −CN)(CC−C 6 H 5 −COO−Cholesterol), are described and designated as PE1-CN-Chol. Polarized optical microscopy, differential scanning calorimetry, and wide-angle X-ray scattering experiments show room temperature glassy/ crystalline texture with crystal formation upon heating to 165 °C. Further heating results in conversion to cholesteric phase. Cooling to room temperature leads to the formation of a cholesteric liquid crystal glass. Scanning tunneling microscopy of a PE1-CN-Chol monolayer reveals self-assembly at the solid−liquid interface with an array of two molecules arranged in pairs, oriented head-to-head through the CN groups, giving rise to a lamella arrangement. The lamella structure obtained from molecular dynamics calculations shows a clear phase separation between the conjugated platinum acetylide and the hydrophobic cholesterol moiety with the lamellae separation distance being 4.0 nm. Ultrafast transient absorption and flash photolysis spectra of the glass show intersystem crossing to the triplet state occurring within 100 ps following excitation. The triplet decay time of the film compared to aerated and deoxygenated solutions is consistent with oxygen quenching at the film surface but not within the film. The high chromophore concentration, high glass thermal stability, and long triplet lifetime in air show that these materials have potential as nonlinear absorbing materials.

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Synthesis, optical and structural properties of sanidic liquid crystal (cholesteryl)benzoate-ethynylene oligomers and polymer

Cited by 20 publications

References 40 publications

Dual Emission of meso‐Phenyleneethynylene–BODIPY Oligomers: Synthesis, Photophysics, and Theoretical Optoelectronic Study

Dual Emission of meso‐Phenyleneethynylene–BODIPY Oligomers: Synthesis, Photophysics, and Theoretical Optoelectronic Study

A Portrait of the OPE as a Biological Agent

Nanoscale Organization of a Platinum(II) Acetylide Cholesteric Liquid Crystal Molecular Glass for Photonics Applications

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