Expanding the Chemical Space of Tetracyanobuta‐1,3‐diene (TCBD) through a Cyano‐Diels‐Alder Reaction: Synthesis, Structure, and Physicochemical Properties of an Anthryl‐fused‐TCBD Derivative

Mateo, Luis M.; Sagresti, Luca; Luo, Yusen; Guldi, Dirk M.; Torres, Tomás; Brancato, Giuseppe; Bottari, Giovanni

doi:10.1002/chem.202103079

Cited by 8 publications

(2 citation statements)

References 53 publications

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“…The reaction of the anthracene derivative 39 , wherein a DMA–ethynyl group is introduced at the 9-position, with TCNE at 40 °C in THF yielded the corresponding TCBD 40 with 91% yield. Subsequent heating of 40 in toluene at 70 °C led to an intramolecular cyano-DA (CDA) reaction, which quantitatively afforded the CDA product 41 ( Scheme 15 ) [ 119 ]. The quantitative CDA reaction progression was attributed to be due to the presence of multiple cyano groups on the skeleton, which increased the dienophile character of the cyano groups and stabilized the structure of the product.…”

Section: Reviewmentioning

confidence: 99%

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Yamada

2024

Beilstein J. Org. Chem.

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Various push–pull chromophores can be synthesized in a single and atom-economical step through [2 + 2] cycloaddition–retroelectrocyclization (CA–RE) reactions involving diverse electron-rich alkynes and electron-deficient alkenes. In this review, a comprehensive investigation of the recent and noteworthy advancements in the research on push–pull chromophores prepared via the [2 + 2] CA–RE reaction is conducted. In particular, an overview of the physicochemical properties of the family of these compounds that have been investigated is provided to clarify their potential for future applications.

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Section: Reviewmentioning

confidence: 99%

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Yamada

2024

Beilstein J. Org. Chem.

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“…The CA - RE reaction ,,− is also versatile for the PSM, as various electron-deficient alkene reactants ( i.e. , besides TCNE) can be tested on the amine-activated backbone alkynes, and the resulting push–pull groups can also undergo further transformations − to broaden the functional scope.…”

Section: Introductionmentioning

confidence: 99%

Minimalist Design for Solar Energy Conversion: Revamping the π-Grid of an Organic Framework into Open-Shell Superabsorbers

Liu

Zhong

et al. 2023

JACS Au

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We apply a versatile reaction to a versatile solid: the former involves the electron-deficient alkene tetracyanoethylene (TCNE) as the guest reactant; the latter consists of stacked 2D honeycomb covalent networks based on the electron-rich βketoenamine hinges that also activate the conjugated, connecting alkyne units. The TCNE/alkyne reaction is a [2 + 2] cycloaddition−retroelectrocyclization (CA-RE) that forms strong push− pull units directly into the backbone of the framework�i.e., using only the minimalist "bare-bones" scaffold, without the need for additional side groups of alkynes or other functions. The ability of the stacked alkyne units (i.e., as part of the honeycomb mass) to undergo such extensive rearrangement highlights the structural flexibility of these covalent organic framework (COF) hosts. The COF solids remain porous, crystalline, and air-/water-stable after the CA-RE modification, while the resulting push−pull units feature distinct open-shell/free-radical character, are strongly light-absorbing, and shift the absorption ends from 590 nm to around 1900 nm (band gaps from 2.17−2.23 to 0.87−0.95 eV), so as to better capture sunlight (especially the infrared region which takes up 52% of the solar energy). As a result, the modified COF materials achieve the highest photothermal conversion performances, holding promise in thermoelectric power generation and solar steam generation (e.g., with solar-vapor conversion efficiencies >96%).

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Donor‐Acceptor Based 1,8‐Naphthalimide Substituted Phenothiazines: Tuning of HOMO‐LUMO Gap

2021

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A set of donor-acceptor (D-A) substituted phenothiazine based chromophores (D-π-D-π-A, D'-π-D-π-A, D-A'-D-π-A and D'-A'-D-π-A) were designed and synthesized. The phenothiazine was substituted with the 4-ethynyl-1,8-naphthalimide (NPI) on one side and a variety of donors (phenothiazine, carbazole, ferrocene and triphenylamine) were introduced on the other side of phenothiazine via Pdcatalyzed Sonogashira cross-coupling reaction resulting PTZ8-11. In order to tune the optoelectronic properties of the phenothiazine chromophores, cyano-based acceptor 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) was incorporated by [2 + 2] cycloaddition-electrocyclic ring-opening reaction of phenothiazine derivatives PTZs 8-11 and tetracyanoethylene (TCNE). The photophysical and electrochemical studies showed that the incorporation of TCBD acceptor in the phenothiazine chromophores PTZs 12-15 facilitated the donor-acceptor strength to greater extent. The electronic absorption spectra exhibited red shifted absorption bands for the TCBD substituted phenothiazines as compared to the alkynylated phenothiazines which led to much lower optical band gaps in the formers. The experimental values were also supported by the DFT and TD-DFT calculations.

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Expanding the Chemical Space of Tetracyanobuta‐1,3‐diene (TCBD) through a Cyano‐Diels‐Alder Reaction: Synthesis, Structure, and Physicochemical Properties of an Anthryl‐fused‐TCBD Derivative

Abstract: Dedicated to Professor Ulrich Nickel on the occasion of his 80th birthday.

Cited by 8 publications

References 53 publications

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Minimalist Design for Solar Energy Conversion: Revamping the π-Grid of an Organic Framework into Open-Shell Superabsorbers

Donor‐Acceptor Based 1,8‐Naphthalimide Substituted Phenothiazines: Tuning of HOMO‐LUMO Gap

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