Enabling Room-Temperature Mechanochromic Activation in a Glassy Polymer: Synthesis and Characterization of Spiropyran Polycarbonate

Vidavsky, Yuval; Yang, Steven J.; Abel, Brooks A.; Agami, Iris; Diesendruck, Charles E.; Coates, Geoffrey W.; Silberstein, Meredith N.

doi:10.1021/jacs.9b04229

Cited by 72 publications

(67 citation statements)

References 54 publications

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“…The substitution pattern that allows to trigger the mechanically induced SP→MC isomerization at smallest force or stress includes 6‐NO 2 functionalization and polymer chain linkage at carbon C 8 (ortho to oxygen) at the pyran half. [ 15,35–39,42,53 ] This result was later on confirmed by a study from Barbee et al. using single chain force spectroscopy on high molecular weight SP copolymers made by ring opening metathesis polymerization (ROMP) with different substituents at C 6 .…”

Section: Effect Of Sp Substituents On the Mechanochromism Of Sp‐functmentioning

confidence: 77%

“…[15,35,36] SP derivatives can be used in form of bifunctional initiators for controlled radical and ring opening polymerizations, [15,37] cross-linkers for hydrosilylation, [36] ring monomers for ring opening metathesis polymerization [38] or bifunctional monomers for polyaddition and polycondensation reactions. [39][40][41][42] Main chain copolymers made by chemistries that allow for the incorporation of more than one SP unit are intriguing materials that make up a subclass next to polymers with a single SP unit at the chain's midpoint (Figure 1a-c). [8,28,40] A higher SP content with statistically or alternating SP copolymers, or even homopolymers, potentially enable cooperative effects and properties not attainable with polymers having single SP units.…”

Section: Sp Derivatization By Direct Incorporation Into Main Chain Pomentioning

confidence: 99%

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Substituent Effects Control Spiropyran–Merocyanine Equilibria and Mechanochromic Utility

Sommer

2020

Macromol. Rapid Commun.

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From a microscopic point of view, CC bond cleavage produces radicals which may undergo secondary reactions that further destabilize polymeric materials. Thus, for a long time, such mechanicallyinduced bond scission and degradation has been treated in negative context, as these reactions occurred in an uncontrolled way, at undefined positions at the polymer chain and usually caused property profiles of lower quality. The view on mechanically-induced chemical reactions has meanwhile changed, with mechanochemistry [6,7] being nowadays a vital field that aims at exploiting mechanical force as a form of energy to trigger chemical reactions, which yield product distributions that may or may not differ compared to heat-and light-induced reactions. [8] A prime example in the area of polymer mechanochemistry includes mechanically induced metal-ligand bond scission [9] that gives rise to mechano-catalysis, as pioneered by the Sijbesma group. [10,11] Work by Hickenboth et al. has investigated a force-induced pericyclic ring opening reaction which furnished different product distributions compared to what is obtained according to the Woodward-Hoffman rules. [12] Polymers are ideal for this purpose as stress transduction to the molecular level is easily achieved using solution sonication or bulk mechanical testing. If a mechanically-induced reaction leads to changes in optical properties, the material is termed mechanochromic. The structural unit undergoing optical changes upon mechanical activation is called mechanophore. [13] In 2001, Tipikin et al. observed that grinding a spiropyran (SP) small molecule produces the corresponding merocyanine (MC) and thus a color change. [14] The force-induced SP→MC isomerization by using polymers with SP units covalently incorporated at their mid points was pioneered by Moore et al. using sonication and later on by Sottos et al. using classical stress-strain experiments of bulk specimens. [13,15] Their pioneering works initiated a large number of studies, not only in the area of SP containing polymers but also related to the development of other mechanophores, in the areas of mechanochemistry and mechanochromic polymers. Since then SPs are popular mechanophores despite their multiple isomers and conformers. [16-19] It is interesting to note that the two positions of polymer linkage at SP, which are meanwhile considered most efficient for mechanoactivation, have been used by Smeets et al. as early as 1974 to Spiropyran (SP) derivatives can be converted into the colored merocyanine (MC) form using a variety of triggers. Optical switching by light for memories and dynamic systems is long known. Recently, mechanical force has been reported as an additional stimulus that converts SP into MC. SP-based mechanochromic systems are especially interesting for polymer scientists, as the covalent attachment of polymer chains is ideal to transduce force to the SP level. Whether such materials are investigated to better understand fundamental processes or long standing questions in polymer science, to ...

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Section: Effect Of Sp Substituents On the Mechanochromism Of Sp‐functmentioning

confidence: 77%

Section: Sp Derivatization By Direct Incorporation Into Main Chain Pomentioning

confidence: 99%

Substituent Effects Control Spiropyran–Merocyanine Equilibria and Mechanochromic Utility

Sommer

2020

Macromol. Rapid Commun.

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“…This advance will allow us to probe a much broader range of strain conditions with mechanochromism, from very small to large deformations, as well as provide intriguing insights on the process of mechanotransduction, by which force is transferred from the macroscopic to microscopic and nanoscopic length scales. We envision that this system or similar materials could also find application as laminate mechano‐reporters for a wider range of polymeric materials; [ 45,46 ] moreover, while the work here has focused on tension and indentation, other modes of mechanical deformation, such as shear, [ 32,47,48 ] could conceivably be imaged with these materials. Future developments of an even more deformable photonic array with a wider dynamic mechanical range, as well as a mechanochemical component responsive to smaller forces such as a supramolecular mechanophore, would enable the creation of more detailed mechanographs, with both local stress and strain information in a single deformation state.…”

Section: Resultsmentioning

confidence: 99%

Cephalopod‐Inspired High Dynamic Range Mechano‐Imaging in Polymeric Materials

Clough

Gucht

Kodger

et al. 2020

Adv Funct Materials

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Cephalopods, such as squid, cuttlefish, and octopuses, use an array of responsive absorptive and photonic dermal structures to achieve rapid and reversible color changes for spectacular camouflage and signaling displays. Challenges remain in designing synthetic soft materials with similar multiple and dynamic responsivity for the development of optical sensors for the sensitive detection of mechanical stresses and strains. Here, a high dynamic range mechano‐imaging (HDR‐MI) polymeric material integrating physical and chemical mechanochromism is designed providing a continuous optical read‐out of strain upon mechanical deformation. By combining a colloidal photonic array with a mechanically responsive dye, the material architecture significantly improves the mechanochromic sensitivity, which is moreover readily tuned, and expands the range of detectable strains and stresses at both microscopic and nanoscopic length scales. This multi‐functional material is highlighted by creating detailed HDR mechanographs of membrane deformation and around defects using a low‐cost hyperspectral camera, which is found to be in excellent agreement with the results of finite element simulations. This multi‐scale approach to mechano‐sensing and ‐imaging provides a platform to develop mechanochromic composites with high sensitivity and high dynamic mechanical range.

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“…Recent reviews on the application of the AIE technology in the sensing field well evidence the active and growing interest of the scientific community on this topic [29,30,31,32,33,34,35,36,37,38,39]. As far as external solicitations are concerned, those derived by mechanical stress results are of the most investigated so far [40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55]. Mechanical forces are present every day in nature, and consist in pressure, shearing force, friction and stress, all of them possibly accountable for damages in macroscopic materials that are generally detectable with invasive or destructive sensing applications.…”

Section: Introductionmentioning

confidence: 99%

Mechanochromic Fluorescent Polymers with Aggregation-Induced Emission Features

Pucci

2019

Sensors

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Mechanochromic polymers are defined as materials that are able to detect a mechanical stress through an optical output. This feature has evoked a growing interest in the last decades, thanks to the progress of chromogenic molecules whose optical characteristics and chemical functionalities allow their effective insertion in many thermoplastic and thermoset matrices. Among the different types of fluorogenic probes able to detect mechanical solicitations, those with aggregation-induced emission (i.e., AIEgens) have attracted tremendous interest since their discovery in 2001. In the present review, the main principles behind the AIEgens working behavior are introduced along with the current state of knowledge concerning the design and preparation of the derived mechanochromic fluorescent polymers. Examples are provided concerning the most ingenious solution for the preparation of chromogenic materials, starting from different types of commodity plastics or synthetic polymers and combined with the latest AIE technology to provide the most sensitive response to mechanical stress.

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Enabling Room-Temperature Mechanochromic Activation in a Glassy Polymer: Synthesis and Characterization of Spiropyran Polycarbonate

Cited by 72 publications

References 54 publications

Substituent Effects Control Spiropyran–Merocyanine Equilibria and Mechanochromic Utility

Substituent Effects Control Spiropyran–Merocyanine Equilibria and Mechanochromic Utility

Cephalopod‐Inspired High Dynamic Range Mechano‐Imaging in Polymeric Materials

Mechanochromic Fluorescent Polymers with Aggregation-Induced Emission Features

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