Strain visualization for strained macrocycles

Colwell, Curtis; Price, Tavis W.; Stauch, Tim; Jasti, Ramesh

doi:10.1039/d0sc00629g

Cited by 100 publications

(101 citation statements)

References 53 publications

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“…StrainViz was performed using the available soware with the same functional and basis set. 26 Nuclear independent chemical shi (NICS) was calculated using aroma with 6-311+G* basis set and B3LYP functional. All calculations were performed using Gaussian-09 suite.…”

Section: Methodsmentioning

confidence: 99%

Effect of curvature and placement of donor and acceptor units in cycloparaphenylenes: a computational study

et al. 2020

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Section: Methodsmentioning

confidence: 99%

Effect of curvature and placement of donor and acceptor units in cycloparaphenylenes: a computational study

et al. 2020

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“…Considering that the efficiency of flex‐activation commonly lies below 10 %, [24,25] detailed insights into the activation mechanism are direly needed, since this knowledge would allow the optimization of this process. In this study, the mechanism of flex‐activation in mechanophores is elucidated using quantum mechanochemical methods, [27–29] which have been used successfully in the past to, e. g., study the debated cycloreversion of triazoles, [30–32] develop novel molecular subunits for stress‐sensing in polymers, [33–37] and investigate the impact of topological effects on mechanical properties and the reactivity of molecules [38–40] …”

Section: Methodsmentioning

confidence: 99%

The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry

et al. 2020

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Flex‐activated mechanophores can be used for small‐molecule release in polymers under tension by rupture of covalent bonds that are orthogonal to the polymer main chain. Using static and dynamic quantum chemical methods, we here juxtapose three different mechanical deformation modes in flex‐activated mechanophores (end‐to‐end stretching, direct pulling of the scissile bonds, bond angle bendings) with the aim of proposing ways to optimize the efficiency of flex‐activation in experiments. It is found that end‐to‐end stretching, which is a traditional approach to activate mechanophores in polymers, does not trigger flex‐activation, whereas direct pulling of the scissile bonds or displacement of adjacent bond angles are efficient methods to achieve this goal. Based on the structural, energetic and electronic effects responsible for these observations, we propose ways of weakening the scissile bonds experimentally to increase the efficiency of flex‐activation.

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“…To quantify the strain energy in BT [10]CPP and BT [8]CPP, a strain analysis program (StrainViz) recently developed by our group was employed. [44] The total strain of each BTcontaining CPP is almost identical to the analogous [n]CPP ( Figure S13). [10]CPP has a total strain of 57.4 kcal mol À1 vs. 55.6 kcal mol À1 for BT [10]CPP.…”

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confidence: 89%

Synthesis, Characterization, and Computational Investigation of Bright Orange‐Emitting Benzothiadiazole [10]Cycloparaphenylene

2020

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Conjugated aromatic macrocycles are attractive due to their unique photophysical and optoelectronic properties. In particular, the cyclic radially oriented π‐system of cycloparaphenylenes (CPPs) gives rise to photophysical properties unlike any other small molecule or carbon nanomaterial. CPPs have tunable emission, possess large extinction coefficients, wide effective Stokes shifts, and high quantum yields. However, accessing bright CPPs with emissions beyond 500 nm remains difficult. Herein, we present a novel and bright orange‐emitting CPP‐based fluorophore showing a dramatic 105 nm red‐shift in emission and striking 237 nm effective Stokes shift while retaining a large quantum yield of 0.59. We postulate, and experimentally and theoretically support, that the quantum yield remains large due to the lack of intramolecular charge transfer.

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Strain visualization for strained macrocycles

Abstract: Strain has a unique and sometimes unpredictable impact on the properties and reactivity of molecules.

Cited by 100 publications

References 53 publications

Effect of curvature and placement of donor and acceptor units in cycloparaphenylenes: a computational study

Effect of curvature and placement of donor and acceptor units in cycloparaphenylenes: a computational study

The Mechanism of Flex‐Activation in Mechanophores Revealed By Quantum Chemistry

Synthesis, Characterization, and Computational Investigation of Bright Orange‐Emitting Benzothiadiazole [10]Cycloparaphenylene

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