Phenyl Ethynyl Research Articles

Innovative thermal crosslinked polyimide gas separation membrane with highly selective and resistance to physical aging base on phenyl ethynyl

In this study, a high performance phenyl ethynyl thermal crosslinked 6FDA-based polyimide (CR-4ETA-x) was developed, which has high gas permeability and selectivity, resistance to physical aging. By introducing 4,4′-(Acetylene-1,2-diyl) diphthalic anhydride (4ETA) monomer into the polyimide structure, the thermal crosslinking precursor membrane was formed. The precursor membrane was heat treated at 440℃ to obtain CR-4ETA-x. After heat treatment, we detected the olefin radical in the crosslinked membrane by electron paramagnetic resonance, which proved that the polyimide network was formed. This allows the crosslinked membrane to have greater d-spacing, higher rigidity, and BET surface area. The CO2 permeability of CR-4ETA-5% is 4114 barrer and the CO2/CH4 selectivity is 19.22. Compared to 6FDA-DAM, the CO2 permeability increased by 477% while the selectivity decreased by only 17%. CR-4ETA-20% shows the CO2 permeability of 3560 Barrer and CO2/CH4 selectivity of 21.1 in CO2/CH4 mixed-gas. After 60 days of aging the permeability maintenance of CR-4ETA-20% were 88%, 84%, 83% and 91% for O2, N2, CO2 and CH4. In addition, in the long-term stability test of more than 100 h, the separation performance of CR-4ETA-20% did not decrease significantly. However, CR-4ETA-x also has limitations, such as poor stability in alkaline environments and lower gas permeability than some advanced carbon molecular sieve membranes. In general, the method of phenyl ethynyl thermal crosslinking provides an effective way for the development of CO2 separation membranes with possible applications.

Synthesis and Optical Properties of Binaphthyl Derivatives with Comprehensive Introduction of Phenylethynyl Groups.

In this study, compounds with phenylethynyl (PE) groups introduced at all of the possible positions of the methylene-bridged structure of the 1,1'-bi-2-naphthol backbone (3-PE to 8-PE) were synthesized. Compounds with four or six phenylethynyl groups (3,6-PE, 4,6-PE, 5,6-PE, 6,7-PE, and 3,4,6-PE) were also synthesized. The key reaction for the synthesis of these compounds was the Sonogashira reaction using halogen scaffolds. The new transformation methods include (1) selective bromination of the 5-position of the binaphthyl skeleton and (2) bromination of the 6-position and then iodination of the 4-position, followed by the Sonogashira reaction of iodine at the 4-position and lithiation and protonation of bromine at the 6-position. The optical properties of the compounds were evaluated. The extension of the π system greatly differed depending on the position of the phenylethynyl group. 4-PE, 4,6-PE, and 3,4,6-PE, in which the phenylethynyl groups were introduced in the extended direction of the naphthalene linkage axis, showed longer absorption and emission wavelengths and higher fluorescence quantum yields than the other compounds. In circularly polarized luminescence measurements, 7-PE showed a relatively large glum value, an interesting finding that reverses the sense.

Bromine substituent position of tetraphenylethylene-based luminogens effect on enhanced AIE and reversible mechanofluorochromic properties by halogen bonding

The halogen atoms have been exploited for designing highly efficient aggregation-induced emission (AIE) materials in recent years, whereas the development of halogenated AIEgen has been greatly limited by the unclear inherent mechanism. In this paper, a series of 1,1,2,2-tetrakis (4-(phenyl ethynyl) phenyl) ethene (TPPE) derivatives with bromine (Br) substituents in different positions were synthesized and their unique photophysical behaviors based on the anti-heavy atom effect were investigated. The brominated TPPE derivatives possessed higher fluorescence quantum yield (ФF) than that of TPPE, resulting from the formation of intermolecular Br-based bonds. Single crystal analysis and theoretical calculations revealed that changing the positions of the Br substituents could induce the formation of different intermolecular interactions. The Br-based bonds efficiently restricted the intermolecular motion, in which the Br⋯Br bond made a decisive factor in determining the highly efficient fluorescence. TPPE derivatives displayed obvious mechanofluorochromic (MFC) properties. PXRD and SEM results demonstrated that the crystal-to-amorphous transition attributed to the reversibility of MFC properties. This work provides a straightforward and practical method to achieve highly efficient AIE-active materials with higher contrast MFC properties via introducing the halogen atoms.

Coordination of hydrogen-bonding and π–π stacking induced elasticity and efficient optical-waveguiding in 4,7-bis(phenyl ethynyl)benzo[c][1,2,5] thiadiazole-based crystals

Hydrogen bonding and π–π stacking were combined in a single component, inducing elasticity and efficient optical waveguiding properties in crystals.

Effect of the charge-separated state on the 3MLCT state: Synthesis and study of the photophysics of electron donor-acceptor dyads based on Pt(II)-Schiff base coordination framework and naphthalenediimide chromophore

We prepared Pt(II)-Salen Schiff base complexes with a naphthalenediimide (NDI) unit attached on the coordination framework, to study the intersystem crossing (ISC), the charge separation, and the possible formation of a long-lived triplet charge separated (CS) state. The Pt(II)-Schiff base coordination framework acts as electron donor and it shows ultrafast ISC (<1 ps) and small Stokes shift. NDI acts as electron acceptor. The two units are attached either via a phenyl linker (Pt-NDI) or phenyl ethynyl linker (Pt-CC-NDI). Negligible electronic interaction between the Pt(II)-Schiff base coordination framework and the NDI unit at ground state was observed for both dyads, whereas the phosphorescence of the Pt(II)-Schiff base coordinated framework was quenched to large extent in the dyads, as compared to the reference complexes containing no NDI unit, especially in polar solvents. Electrochemical and optical spectral data show that the CS state energy is 1.93 eV, 1.82 eV, 1.54 eV, 1.43 eV in n-hexane (HEX), toluene (TOL), tetrahydrofuran (THF), acetonitrile (ACN), respectively. In comparison, the 3MLCT state and 3NDI state energy are 1.97 and 2.04 eV, respectively. Nanosecond transient absorption spectra show the formation of the 3MLCT state for Pt-CC-NDI, whose lifetimes is shortened in polar solvents (τT = 3.5 µs, 2.1 µs, 22 ns, and 19 ns in HEX, TOL, THF and ACN, respectively), similar trend was observed for Pt-NDI. Femtosecond transient absorption spectra show that the charge separation takes less than 1 ps both in toluene and acetonitrile. Quenching of the otherwise long-lived triplet excited state (3.5 µs) by a short lived CS state may be developed as a photo-protection mechanism similar to that found in natural photosynthetic apparatus.

Does alkyl chain unsaturation affect tunability of the aryl alkyl imidazolium‐based ion pairs?

AbstractThree series of functionalized ion pairs composed of ethyl phenyl imidazolium [PhIM(C2H5)]+, (vinyl) ethenyl phenyl imidazolium [PhIM(C2H3)]+and ethynyl phenyl imidazolium [PhIM(C2H)]+cations and acetate ([Y1]−), nitrate ([Y2]−), tetrafluoroborate ([Y3]−) and perchlorate ([Y4]−) anions were designed and their physical and chemical properties were analyzed at M06‐2X‐GD3/AUG‐cc‐pVDZ level of theory. The effect of alkyl chain unsaturation on structural characteristics, energetic parameters, electronic and topological properties, and the global reactivity parameters and also on some physical and chemical properties such as dipole moment, melting point, and electrochemical window of the introduced IPs was discussed. Based on electrochemical window values, the studied IPs including alkyl chain unsaturation in the cation and [Y1‐2]−anions have no suitable electrochemical stability for use in electrochemical devices.

Regioselective 2,3-disubstituted porphyrins: synthesis, spectral, structural and electrochemical properties

Regioselective β-disubstituted meso-tetraphenylporphyrins, H2TPP(X)2 (X = methyl (CH3), phenyl (Ph), bromo (Br), phenylethynyl (PE)), and their metal complexes (Cu(ii), Co(ii), Ni(ii), Zn(ii)) were synthesized/characterized using various techniques.

Activated porous carbon derived from ethynyl phenyl azo phenol-biphenylene resin for high-performance supercapacitor

Activated porous carbon derived from ethynyl phenyl azo phenol-biphenylene resin for high-performance supercapacitor

Synthesis of 5'-Thymidine-Conjugated Formylphenylboronic Acids as Potential Lysine Targeting Iminoboronate Reversible Covalent Enzyme Probes.

The design of reversible-covalent molecules to selectively target the ε-amino functionality of lysine residues in enzymes or proteins is a highly desirable goal. Herein, we describe synthetic methodology used to prepare a series of 5'-thymidine-linked formylphenylboronic acids as probes to interrogate sugar nucleotide processing enzymes that recognize thymidine. The first synthetic strategy mitigated the need for protecting group manipulations of thymidine by capitalizing upon the straightforward preparation, isolation, and reactivity of 5'-azidothymidine. An alkyne cycloaddition partner was installed through either a propargyl or ethynyl phenyl ketone derived boronic acid. The second strategy directly linked formylphenylboronic acids to 5-thymidine through an ether linkage installed using Mitsunobu conditions with 3'-O,3-dibenzoylthymidine. Iminoboronate formation was observed with a selected probe.

Artesunate Alleviates Paclitaxel-Induced Neuropathic Pain in Mice by Decreasing Metabotropic Glutamate Receptor 5 Activity and Neuroinflammation in Primary Sensory Neurons.

Experimental studies on the pathogenetic process of paclitaxel-induced neuropathic pain (PINP) have been initially carried out, but PINP still has no effective therapy. Recently reported studies have highlighted the involvement of glutamate receptors and neuroinflammation in peripheral and central nociceptive transmission in PINP. Artesunate is a first-line antimalarial drug with established efficacy in alleviating pain in a variety of pathologies. The current work assessed whether artesunate inhibits PINP by modulating metabotropic glutamate receptor 5 (mGluR5) and neuroinflammation in mice. The anti-hyperalgesic effect of artesunate was verified by assessing mechanical frequency and thermal latency in the paw withdrawal test as well as spontaneous pain. The expression levels of mGluR5, pain-related receptors and neuroinflammatory markers in dorsal root ganglion (DRG) were examined. In addition, treatment with CHPG and 2-methyl-6-(phenyl ethynyl) pyridine (MPEP) (mGluR5 agonist and antagonist, respectively) was performed to determine mGluR5’s role in the anti-hyperalgesic properties of artesunate. We demonstrated artesunate prevented PINP in a dose-dependent manner, while exerting a clear anti-hyperalgesic effect on already existing PINP. Artesunate normalized paclitaxel-related expression changes in DRG mGluR5, NR1, and GluA2, as well as six paclitaxel related neuroinflammation markers. Intrathecal application of MPEP treated PINP by reversing NR1 and GluA2 expression changes but had no effects on chemokines and inflammatory factors. Furthermore, artesunate treatment reversed acute pain following CHPG application. In conclusion, this study revealed that artesunate alleviates paclitaxel-induced hyperalgesia and spontaneous pain by decreasing DRG mGluR5 expression and neuroinflammation in the mouse model of PINP.

Symmetric vs. asymmetric: Which one is the better molecular configuration for achieving robust NLO response?

The current study reports a comparative investigation for the nonlinear optical (NLO) response for some symmetric and asymmetric molecular configurations. The designed compounds are featuring a similar 2,7-bis(phenyl ethynyl)cyclopentaaceanthrylene core connected to different terminal donor and acceptor moieties such as dimethylamine, methoxy, nitro and ethene-tricarbonitrile groups based on three topologies, “D-π-D” (1–2), “A-π-A” (3–4) and “D-π-A” (5–8). A comparative analysis of these symmetrically and asymmetrically substituted chromophores is done to investigate the effect of different terminal groups on their NLO response, optical and charge transfer properties. The asymmetric compounds display larger first hyperpolarizability amplitudes (β//) than those of the symmetric compounds where a β// amplitude as large as 1851 × 10−30 esu is calculated for asymmetric compound 6. Interestingly, the average second hyperpolarizabilities (γ) for symmetric compound 4 have been calculated to be 16, 096 × 10−36 esu and for asymmetric counterpart compound 6 it is found to be 23, 162 × 10−36 esu using M06/6-311G* methodology. Our findings were also inline with experimental observations of Mathews et al. (Mathews, S.J., et al., 2007. Optics Communications, 280, 206–212), where they also experimentally determined the larger third-order susiptibility for asymmetric phthalocyanine (Pc3) than their symmetric counterparts. Additionally, the NLO polarizabilities of all the compounds have also been compared with a typical donor-acceptor molecule of p-NA to specify the comparison of designed compounds. TD-DFT studies have shown that the higher β and γ values were found for asymmetric compounds owing to their lower transition energies and larger trasition dipole moments. The depiction of molecular orbitals and electrostatic potentials have shown more efficient intramolecular charge transfer (ICT) for asymmetric compounds leading to the robust NLO response. Thus, a systematic comparison of the NLO polarizabilities and other electronic properties of our designed symmetric and asymmetric compounds shows that symmetry based designing of NLO compounds are very crucial to get robust NLO response properties.

Synthesis, Photophysical and Electrochemical Studies of Β-Disubstituted Silver Corroles

β-Substituted corroles have been widely used in variety of applications and exhibit unique electronic and photophysical properties [1]. π-Extension at the β-position using functional groups such as phenylethynyl or pyrrolopyrazino induces intriguing stability and planarity of the macrocyclic core [2]. Keeping this in mind, a series of β-disubstituted silver tritolylcorroles (R2[TTC]Ag) have been synthesized via Pd-catalyzed reactions in good to excellent yields (Fig. 1a). Herein we are trying to investigate the effect of the various β-substituents such as methyl (Me), phenyl (Ph), methyl acrylate (MA) and phenylethynyl (PE) on photophysical and electrochemical properties. In cyclic voltammetric studies, the first oxidation potential of Me2[TTC]Ag 2 decreases (cathodic shift) by 70 mV compared to [TTC]Ag due the inductive effect of two methyl groups while in case of (MA)2[TTC]Ag 4, there is large anodic shift (170 mV) in the first oxidation potential probably due to strong electron withdrawing effect of two methyl acrylate group compared to 2 (Fig. 1b). Complex 4 depicted very high dipole moment (10.31 D), which could be utilized in NLO studies (Fig. 1c). We have investigated the effect of both electron-accepting and -donating substituents through single, double and triple bond on the macrocyclic ring using photophysical, theoretical and electrochemical studies. Complexes (2-5) exhibited remarkable broadening and increase in the intensity of red shifts of soret and Q bands of absorption spectra. Here, we have synthesized corroles with side extension of π-arm which helps in shifting of Q bands towards NIR region which could be helpful in PDT or optoelectronic applications. Figure 1. (a) Molecular structures of R2[TTC]Ag; (b) Comparative Cyclic voltammograms (CVs) of [TPC]Ag, Me2[TTC]Ag and MA2[TTC]Ag complexes in CH2Cl2 at 298 K under argon atmosphere; (c) The directions of calculated dipole moment of MA2[TTC]Ag. References (a) R. Mishra, B. Basumatary, R. Singhal, G. D. Sharma and J. Sankar, ACS Appl. Mater. Interfaces 2018, 10, 31462–31471; (b) S. Gonglach, S. Paul, M. Haas, F. Pillwein, S. S. Sreejith, S. Barman, R. De, S. Müllegger, P. Gerschel, U. P. Apfel, H. Coskun, A. Aljabour, P. Stadler, W. Schöfberger and S. Roy, Commun. 2019, 10, 1–10; (c) W. Sinha, A. Mahammed, N. Fridman, Z. Gross, ACS Catal., 2020, 10, 3764–3772; (d) R. F. Einrem, A. B. Alemayehu, S. M. Borisov, A. Ghosh, O. A. Gederaas, ACS Omega 2020, 5, 10596–10601.(a) P. Yadav, M. Sankar, X. Ke, L. Cong, K. M. Kadish, Dalton Trans. 2017, 46, 10014–10022; (b) M. Stefanelli, M. L. Naitana, M. Chiarini, S. Nardis, A. Ricci, F. R. Fronczek, C. Lo Sterzo, K. M. Smith, R. Paolesse, J. Org. Chem. 2015, 2015, 6811–6816; (c) B. Berionni Berna, S. Nardis, P. Galloni, A. Savoldelli, M. Stefanelli, F. R. Fronczek, K. M. Smith, R. Paolesse, Org. Lett. 2016, 18, 3318–3321. Figure 1

Investigations of Donor–Acceptor Interactions in 1,3,5-Tris-(3-Methoxy & 3-Methyl Carboxy) Phenyl Ethynyl Benzene Derivatives Using Experimental and DFT Study

Two new 1,3,5-tris-(3-methoxy (6a) & 3-methyl carboxy (6b)) phenyl ethynyl benzene derivatives were synthesized from 1,3,5-triethynylbenze and 3-bromo anisole/methyl-3-bromo benzoate, respectively, under Sonogashira cross-coupling reaction conditions. The molecular structures of these two compounds were confirmed by spectral, CHN, and single-crystal XRD analysis. The compound 6a, crystallized in triclinic system (Space group = Pî, Z = 2, a (Å) = 8.4849(1); b (Å) = 12.0292(2); c (Å) = 12.9601(2); α(°) = 95.580(1); β(°) = 93.170(1); γ (°) = 99.942(1)) and 6b, crystallized in monoclinic system (Space group = P21/n, Z = 4, a (Å) = 3.9282(6); b (Å) = 32.274(1); c (Å) = 27.440(2); β(°) = 92.29(1)). Furthermore, the optimized molecular geometries were compared with experimental counter parts employing DFT approach. The complete spectroscopic studies of the titled compounds were carried out using analytical techniques, such as FT-IR, NMR, CV, and UV–VIS analysis and compared with the theoretical results. The first order hyper-polarizability, natural bond orbital analysis, frontier molecular orbitals, and molecular electrostatic potentials were performed on 6a&b, by employing the DFT method and compared with their ortho- and para-substituent compounds. These results indicated that the two compounds 6a&b, showed different donor–acceptor (D–A) interactions based on donor (−OCH3) or acceptor (–COOCH3) moieties attached to the benzene ring.

β-Disubstituted silver(III) corroles: Facile synthesis, photophysical and electrochemical redox properties

Facile synthesis of 3,17-disubstituted Ag(III) tritolylcorroles (2-5), R2[TTC]Ag where R = methyl (2), phenyl (3), methyl acrylate (MA) (4) and phenylethynyl (PE) (5) using Pd-catalyzed reactions in good to excellent yields are reported. All synthesized corroles were characterized by various spectroscopic techniques and mass spectrometry. MA2[TTC]Ag (4) and PE2[TTC]Ag (5) exhibited highly red-shifted electronic spectral bands with considerable broadening due to extended [Formula: see text]-conjugation and electron withdrawing effect of [Formula: see text]-substituents. Geometry optimization of these corroles was performed using density functional theory (DFT). Among all, MA2[TTC]Ag (4) exhibited very high dipole moment (10.31 D) which could be the potential candidate for nonlinear optical (NLO) applications. The redox tunability was achieved by substituting electron donating and withdrawing substituents at the [Formula: see text]-positions. Particularly, corroles 4 and 5 exhibited lower HOMO–LUMO gap due to extended [Formula: see text]-conjugation and electron withdrawing [Formula: see text]-substituents.

Molecular engineering of triphenylamine‐based metal‐free organic dyes for dye‐sensitized solar cells

AbstractIn this study, the photovoltaic properties of the organic dyes based on triphenylamine having a D‐π‐A structure including TC201, TC202, TC203, TC601, H‐P, F‐P, FF‐P, T‐F, and P1B were investigated theoretically. In this model, triphenylamine was used as an electron donor, cyanoacrylic acid, and benzoic acid as the electron acceptors, and anthracene phenyl, anthracene vinyl phenyl, anthracene ethynyl phenyl, ethynyl anthracene phenyl, styryl phenyl, styryl‐2‐fluorophenyl, styryl‐2,6‐difluorophenyl, styryl furan, and styryl as the π‐conjugated systems. The results show that a change in the π‐conjugated system and electron acceptor affect the properties of the dye‐sensitized solar cell (DSSC). Also, TC601 dye having the ethynyl anthracene phenyl π‐conjugated system shows the highest charge transfer distance (DCT) and the least overlap of the electron–hole distribution (S) in comparison with other dyes. Moreover, the presence of a triple bond in the vicinity of triphenylamine increases the resonance effect of the π‐electrons that facilitates the process of charge transfer in this dye. Spectroscopic analysis shows that H‐P and F‐P dyes have the higher molecular absorption coefficients and TC202, TC203, F‐P, and T‐F dyes show a red shift in comparison with other dyes. Moreover, the voltage–current curve of the studied dyes shows that the highest values of the open circuit voltage and short circuit current density are related to P1B and TC601 dyes, respectively. Finally, TC601 and P1B are proposed as the best candidates to be used in the DSSCs due to their maximum incident photon to current conversion efficiency.

Nonlinear stress–strain behavior of unidirectional carbon fiber/ phenyl–ethynyl terminated KAPTON-type polyimide, TriA-X, composites at elevated temperatures

A phenyl–ethynyl terminated polyimide resin based on KAPTON-type backbone structures, ‘TriA-X’, polyimide is promising as a matrix resin of heat-resistant carbon fiber reinforced plastic composites, but its mechanical properties remain unclear. This study examined off-axis stress–strain behavior of unidirectional carbon fiber (CF)/TriA-X polyimide composites under tensile load at room temperature (RT), 100°C, 150°C, and 200°C to elucidate the matrix resin plastic deformation behavior. Comparing the rupture stress and rupture strain of off-axis specimens at RT and 100°C, they decreased concomitantly with increasing test temperature. Comparison of the rupture stress at 100°C, 150°C and 200°C revealed no significant difference in the rupture stress. A one-parameter plasticity model proposed by Chen and Sun with temperature-dependence of the plasticity model parameters elucidated the nonlinear stress–strain behavior. Model results agreed well with the nonlinear stress–strain behaviors of the CF/TriA-X composites at RT, 100°C, 150°C, and 200°C.

β-Functionalized Dibenzoporphyrins with Mixed Substituents Pattern: Facile Synthesis, Structural, Spectral, and Electrochemical Redox Properties.

A new series of mixed β-substituted dibenzoporphyrins were synthesized, and the effect of β-substitution on the spectral and electrochemical redox properties of the macrocycle was elucidated. The synthetic route to β-tetrasubstituted dibenzoporphyrins begins with the regioselective bromination of NiTPP(Benzo)2 to afford NiTPP(Benzo)2Br4, followed by Pd catalyzed coupling reaction to access NiTPP(Benzo)2(R)4 (R = phenyl (Ph) and phenylethynyl (PE)). Synthesized benzoporphyrins exhibited red-shifted absorption spectral features with tunable redox properties. These benzoporphyrins displayed pronounced electronic effects of β-substituents on the macrocyclic skeleton. NiTPP(Benzo)2(PE)4 exhibited the lowest HOMO-LUMO gap among the series due to extended π-conjugation. Intrestingly, metal-centered oxidation of Ni(II)/Ni(III) was observed for NiOPP(Benzo)2 and NiOPP(Benzo)Br2 after an initial conversion of the neutral porphyrin to its dicationic form under electrochemical conditions.

Synthesis and Thermal Properties of Ethynyl Phenyl Azo Phenol-biphenylene Resin.

A novel addition curing ethynyl phenyl azo phenol-biphenylene resin (EPABN) was synthesized by introducing ethynylphenyl group into biphenyl novolac resin (BN) through diazo coupling reaction. Its synthesis reaction and curing mechanism were also proposed. Fourier transform infrared spectroscopy and 1H NMR spectroscopic analysis showed that the ethynylphenyl group was successfully linked to the BN molecular chain. By differential scanning calorimetry analysis, the curing process of EPABN resin was determined to be 150 °C/2 h + 172 °C/2 h + 203 °C/4 h + 255 °C/4 h + 300 °C/4 h. Gel permeation chromatography and elemental analysis showed that the introduction of ethynylphenyl group increased the number-average molecular weight and weight-average molecular weight of EPABN. Thermogravimetric analysis showed that the EPABN resin synthesized under the obtained optimum conditions has excellent heat resistance, ablation resistance, and mechanical properties. Td5 and Td10 of heat resistance of the cured EPABN resin are 463 and 531 °C, respectively, and its residual char yield at 700 and 1000 °C is 78.2% and 72.1%, respectively.

Microwave-assisted synthesis of (2-butyl-5-nitrobenzo[b]furan-3-yl)-[4 (substituted ethynyl)phenyl]methanones

Microwave-assisted synthesis of (2-butyl-5-nitrobenzo[b]furan-3-yl)-[4 (substituted ethynyl)phenyl]methanones

High-Temperature Shape Memory Behavior of Semicrystalline Polyamide Thermosets.

We have explored semicrystalline poly(decamethylene terephthalamide) (PA 10T) based thermosets as single-component high-temperature (>200 °C) shape memory polymers (SMPs). The PA 10T thermosets were prepared from reactive thermoplastic precursors. Reactive phenylethynyl (PE) functionalities were either attached at the chain termini or placed as side groups along the polymer main chain. The shape fixation and recovery performance of the thermoset films were investigated using a rheometer in torsion mode. By controlling the Mn of the reactive oligomers, or the PE concentration of the PE side-group functionalized copolyamides, we were able to design dual-shape memory PA 10T thermosets with a broad recovery temperature range of 227–285 °C. The thermosets based on the 1000 g mol–1 reactive PE precursor and the copolyamide with 15 mol % PE side groups show the highest fixation rate (99%) and recovery rate (≥90%). High temperature triple-shape memory behavior can be achieved as well when we use the melt transition (Tm ≥ 200 °C) and the glass transition (Tg = ∼125 °C) as the two switches. The recovery rate of the two recovery steps are highly dependent on the crystallinity of the thermosets and vary within a wide range of 74%–139% and 40–82% for the two steps, respectively. Reversible shape memory events could also be demonstrated when we perform a forward and backward deformation in a triple shape memory cycle. We also studied the angular recovery velocity as a function of temperature, which provides a thermokinematic picture of the shape recovery process and helps to program for desired shape memory behavior.