High‐Temperature Solid‐State Post‐synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers DOI Creative Commons
Christophe Lescop, Adrien Schlachter,

Chendong Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 19, 2024

A new luminescent Cu(I) tetrametallic metallacycle B is reported that features very rare semi-bridging aqua ligands. When heated markedly above room temperature, this compound undergoes a post-synthetic transformation in the solid-state, affording C. Thermogravimetric analysis, IR spectroscopy and single-crystal X-ray diffraction reveal alteration preserves gross macrocycle structure, but caused by release of coordinated water molecules with concomitant formation cuprophilic interactions. This transition induces shift from eye-perceived green (B) to blue (C) room-temperature luminescence for these molecular solids. Photophysical measurements time-dependent density-functional theory calculations have been conducted identify origins emission properties lying structurally related assemblies, suggest thermally activated delayed fluorescence dominates radiative relaxation pathways. study highlights innovative feature derivatives, offering access stimuli-sensitive materials can witness, posteriori, exceeding critical temperatures their environment.

Language: Английский

The Use of Photocycloaddition Reactions to Drive Mechanical Motions Resembling Humanoid Movements DOI
Yong Wang, Qiaoqiao Zhang, Qi Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 18, 2024

Abstract With the aim of producing a photomechanical material for incorporation in soft microrobots, one‐dimensional diene coordination polymer (CP) [Cd(F‐bpeb)(3‐CBA) 2 ] n ( CP1 , F‐bpeb=4,4′‐((1 E ,1′ )‐(2,5‐difluoro‐1,4‐phenylene)bis(ethene‐2,1‐diyl))dipyridine, 3‐HCBA=3‐chlorobenzoic acid) was synthesized and characterized. Irradiation with ultraviolet (UV) or visible light causes [2+2] photocycloaddition reactions resulting introduction crystal strain which triggers various types movements. Composite films ‐PVA (SC) fabricated by dispersing crystals into polyvinyl alcohol (PVA) solution allow amplification movement so that film strips exhibit fast flexible curling upon photoirradiation. The composite may be cut long rectangular folded to simulate microrobots variety fast, continuous movements resembling human performing gymnastic exercises.

Language: Английский

Citations

7
The Use of Photocycloaddition Reactions to Drive Mechanical Motions Resembling Humanoid Movements DOI
Yong Wang, Qiaoqiao Zhang, Qi Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(38)

Published: June 18, 2024

Abstract With the aim of producing a photomechanical material for incorporation in soft microrobots, one‐dimensional diene coordination polymer (CP) [Cd(F‐bpeb)(3‐CBA) 2 ] n ( CP1 , F‐bpeb=4,4′‐((1 E ,1′ )‐(2,5‐difluoro‐1,4‐phenylene)bis(ethene‐2,1‐diyl))dipyridine, 3‐HCBA=3‐chlorobenzoic acid) was synthesized and characterized. Irradiation with ultraviolet (UV) or visible light causes [2+2] photocycloaddition reactions resulting introduction crystal strain which triggers various types movements. Composite films ‐PVA (SC) fabricated by dispersing crystals into polyvinyl alcohol (PVA) solution allow amplification movement so that film strips exhibit fast flexible curling upon photoirradiation. The composite may be cut long rectangular folded to simulate microrobots variety fast, continuous movements resembling human performing gymnastic exercises.

Language: Английский

Citations

2
Using Chemical Substitution to Engineer Photomechanical Cinnamalmalononitrile Crystals DOI
Thomas J. Gately, Cody J. Perry,

Sophie Weiss

et al.

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(22), P. 9544 - 9555

Published: Nov. 11, 2024

In this work, a combined experiment and theory approach is used to study the cinnamalmalononitrile family of molecules that undergo [2 + 2] photodimerization in solid-state generate photomechanical actuation. Twelve new derivatives are synthesized exhibit two different crystal packing motifs: head-to-head (HH) which stack with phenyl rings on same side stack, head-to-tail (HT) adjacent opposite sides. only observed for HT motif. Attempts identify chemical substitution patterns favor reactive based simple steric electrostatic considerations fail reliably predict packing, fluorination generated both motifs more-or-less random fashion. Empirically, at 3-position favors while 4-position HH packing. Computational modeling suggests tendency or arrangements stems from complex many-body interactions rest lattice. Modeling periodic density functional shows lattice also explain why motif photochemically active inert. Chemical can affect theoretical work output polymorphs. order obtain polymorph, best strategy appears entail placing strong electron-withdrawing group 3-position, we confirm an polymorph 3-trifluoromethyl- highly photosalient crystal, predicted ideal 40 MJ/m3.

Language: Английский

Citations

2
Synthesis and Thiol-Ene Photopolymerization of Bio-Based Hybrid Aromatic–Aliphatic Monomers Derived from Limonene, Cysteamine and Hydroxycinnamic Acid Derivatives DOI Open Access
Ricardo Acosta Ortiz, Jorge Luis Olivares, Roberto Yáñez‐Macías

et al.

Polymers, Journal Year: 2024, Volume and Issue: 16(23), P. 3295 - 3295

Published: Nov. 26, 2024

Three novel bio-based monomers were synthesized through an amidation reaction involving allylated derivatives of coumaric, ferulic and phloretic acid a diamine obtained from thiol-ene coupling between limonene cysteamine. The containing the enone bond cinnamic moiety underwent photoisomerization photocycloaddition reactions upon UV light irradiation. All three photocured via photopolymerization using glycerol-derived trifunctional thiol, resulting in fully poly(amide–thioether)s. polymers derived that contain exhibited glass transition (Tg) temperatures 85 °C when stoichiometric ratio thiol was used, whereas which excess used Tg 61 74 °C. higher polymers, compared with other reported produced photopolymerizations, attributed to combination aromatic rings cycloaliphatic ring limonene, as well presence amide groups polymer, can induce hydrogen bonding. development high represents significant advancement polymer synthesis sector, offering improved performance sustainability.

Language: Английский

Citations

1
High‐Temperature Solid‐State Post‐synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers DOI Creative Commons
Christophe Lescop, Adrien Schlachter,

Chendong Xu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 19, 2024

Abstract A new luminescent Cu(I) tetrametallic metallacycle B is reported that features very rare semi‐bridging aqua ligands. When heated markedly above room temperature, this compound undergoes a post‐synthetic transformation in the solid‐state, affording C . Thermogravimetric analysis, IR spectroscopy and single‐crystal X‐ray diffraction reveal alteration preserves gross macrocycle structure, but caused by release of coordinated water molecules with concomitant formation cuprophilic interactions. This transition induces shift from eye‐perceived green ( ) to blue room‐temperature luminescence for these molecular solids. Photophysical measurements time‐dependent density‐functional theory calculations have been conducted identify origins emission properties lying structurally related assemblies, suggest thermally activated delayed fluorescence dominates radiative relaxation pathways. study highlights innovative feature derivatives, offering access stimuli‐sensitive materials can witness, posteriori, exceeding critical temperatures their environment.

Language: Английский

Citations

0
High‐Temperature Solid‐State Post‐synthetic Modification of Highly Luminescent Cu(I) Metallacycles toward New Luminescent Thermic Tracers DOI Creative Commons
Christophe Lescop, Adrien Schlachter,

Chendong Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 19, 2024

A new luminescent Cu(I) tetrametallic metallacycle B is reported that features very rare semi-bridging aqua ligands. When heated markedly above room temperature, this compound undergoes a post-synthetic transformation in the solid-state, affording C. Thermogravimetric analysis, IR spectroscopy and single-crystal X-ray diffraction reveal alteration preserves gross macrocycle structure, but caused by release of coordinated water molecules with concomitant formation cuprophilic interactions. This transition induces shift from eye-perceived green (B) to blue (C) room-temperature luminescence for these molecular solids. Photophysical measurements time-dependent density-functional theory calculations have been conducted identify origins emission properties lying structurally related assemblies, suggest thermally activated delayed fluorescence dominates radiative relaxation pathways. study highlights innovative feature derivatives, offering access stimuli-sensitive materials can witness, posteriori, exceeding critical temperatures their environment.

Language: Английский

Citations

0