Amidinium–carboxylate salt bridge mediated proton-coupled electron transfer in a donor–acceptor supramolecular system

Ren, Xiaolei; Wang, Xiaohua; Sun, Yuren; Chi, Xiaodong; Mangel, Daniel; Wang, Hongyu; Sessler, Jonathan L.

doi:10.1039/c8qo01408f

Cited by 10 publications

(11 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The association constant (K a ) corresponding to the formation of this complex was calculated to be 1.54 × 10 5 � 1.82 × 10 4 M À 1 (DMSO), leading us to suggest each amidinium-carboxylate interaction is relatively strong in this polar solvent. [10] However, in aqueous media no evidence of binding was seen according to ITC titration test.…”

Section: Resultsmentioning

confidence: 99%

“…The relatively high pKa of amidines, as well as their ability to support hydrogen bonding interactions with carboxylate anions, [10] led us to consider that they could be used to create SOFs containing AIE-active TPE subunits. With such considerations in mind, a series of fluorescent SOFs was constructed via the hetero-self-assembly between an AIE-active TPE tetra-(amidinium) (TPE 4 + ) tecton and various dicarboxylate building blocks (Scheme 1a).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Fluorescent Supramolecular Organic Frameworks Constructed by Amidinium‐Carboxylate Salt Bridges

Jiang

Xie

Duan

et al. 2021

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

We report here a set of fluorescent supramolecular organic frameworks (SOFs) that incorporate aggregationinduced emission (AIE) units within their frameworks. The fluorescent SOFs of this study were constructed by linking the tetraphenylethylene (TPE)-based tetra(amidinium) cation TPE 4 + and aromatic dicarboxylate anions through amidiniumcarboxylate salt bridges. The resulting self-assembled structures are characterized by fluorescence quantum yields in the range of 4.6 ~14 %. This emissive behavior is ascribed to a combination of electrostatic interactions and hydrogen bonds that operate in concert to impede motions that would otherwise lead to excited state energy dissipation. Singlecrystal X-ray diffraction analyses revealed that the length of the dicarboxylate anion bridges has a considerable impact on the structural features of the resulting frameworks. Nevertheless, all SOFs prepared in the context of the present study were found to display emissive features characteristic of TPEbased AIE luminogens with only a modest dependence on the structural specifics being seen. The SOFs reported here could be reversibly "broken up" and "reformed" in response to acid/base stimuli. This reversible structural behavior is consistent with their SOF nature.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Fluorescent Supramolecular Organic Frameworks Constructed by Amidinium‐Carboxylate Salt Bridges

Jiang

Xie

Duan

et al. 2021

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…26–28 In anisole, a nonlinear-least-square analysis of the fluorescence data afforded a binding constant of 1.2 × 10 5 M −1 , which is within the range for amidinium-carboxylate salt bridges. 18,29…”

Section: Resultsmentioning

confidence: 99%

Cascades of energy and electron transfer in a panchromatic absorber

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Compared with the blooming publications on the organic synthetic methodologies promoted by PCET, the professional and deep experimental studies on PCET mechanism for revealing its fundamental rules are relatively rare in China, [151,[172][173][174][175] however, we are glad to see that more publications on theoretical studies have been published from Chinese groups in last five year. [173][174][175][176][177][178][179][180] Further explorations of PCET mechanism including how substrates and reaction conditions influence and regulate the PCET pathways, and so on, may provide novel ideas and methods for current synthetic methodology, and even help chemists discover unexpected patterns of chemical bond forming and breaking. Therefore, future works are supposed to focus on not only the synthetic applications, but also mechanism studies of PCET reactions, including new forms of PCET processes, which should benefit the development of other branches of chemistry.…”

Section: Discussionmentioning

confidence: 98%

Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Zhou¹,

Kong²,

Liu³

2021

Chinese Journal of Organic Chemistry

View full text Add to dashboard Cite

Proton-coupled electron transfer (PCET) reactions are a kind of unconventional redox reactions, which exhibit special reactivities and selectivities due to their unique interdependent electron-proton transfer mechanisms. There are three possible pathways of PCET processes, including stepwise electron transfer followed by proton transfer (ETPT), proton transfer followed by electron transfer (PTET), and concerted pathway in which electron and proton transfer synchronously (CEPT), avoiding intermediates with high energy. These reactions have been playing a key role in numerous areas in organic chemistry, inorganic chemistry, bioorganic chemistry, organometallic and material chemistry, including the redox processes in natural and artificial systems, such as the activation for small molecules. Recently, the application of PCET reactions in organic synthesis has received a great deal of attentions and interests. Being accompanied by the development of electrochemical methods and photocatalysts, more and more novel reactions in electrochemistry and photochemistry involve PCET processes have been reported. Applying these electrochemical and photochemical methods, the activation of X-H bond has been achieved via PCET processes, including C-H bond, N-H bond, P-H bond, S-H bond or O-H bond. Thus, based on these crucial processes, a number of vital structures and fundamental frameworks can be synthesized, and various synthetic building blocks and natural products have been attained. For example, pharmaceutical building blocks like 2°-piperidines can be cyanated at their α-position; substituted dimeric pyrroloindolines such as (-)-calycanthidine, (-)-chimonanthine, and (-)-psychotriasine have also been successfully synthesized via PCET mechanism. Moreover, not only the products of reduction of multiple bonds (C＝ Y bond such as C＝C bond, C＝N bond and C＝O bond), but also the products of self/cross-coupling have been achieved via PCET mechanism. In this review, the recent applications and developments of PCET mechanism in organic synthesis are summarized, including new catalyst systems and new reagents, especially with electrochemical and photochemical methodologies. The future of this area has also been demonstrated from both experimental and theoretical aspects. Keywords proton-coupled electron transfer; organic synthesis; radical reactions; functionalization

show abstract

Amidinium–carboxylate salt bridge mediated proton-coupled electron transfer in a donor–acceptor supramolecular system

Abstract: A supramolecular polymer that allows for intrapolymer proton-coupled photoinduced electron transfer was constructed by means of amidinium-carboxylate salt bridges.

Cited by 10 publications

References 41 publications

Fluorescent Supramolecular Organic Frameworks Constructed by Amidinium‐Carboxylate Salt Bridges

Fluorescent Supramolecular Organic Frameworks Constructed by Amidinium‐Carboxylate Salt Bridges

Cascades of energy and electron transfer in a panchromatic absorber

Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Contact Info

Product

Resources

About