A Highly Stabilized Phosphonium Ylide that Forms Supramolecular Dimers in Solution and the Solid State

Kim, Min Ji; Luo, Stella M.; Greenlee, Andrew J.; Cao, Dennis

doi:10.1002/chem.201904131

Cited by 7 publications

(5 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It should be pointed out that few F-PMDI such as pyridinium-F-PMDI and phosphonium-F-PMDI have been synthesized and widely used in several applications. 50 , 51 …”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Functional Pyromellitic Diimide as a Corrosion Inhibitor for Galvanized Steel: An Atomic-Scale Engineering

et al. 2022

View full text Add to dashboard Cite

Corrosion of metal/steel is a major concern in terms of safety, durability, cost, and environment. We have studied a cost-effective, nontoxic, and environmentally friendly pyromellitic diimide (PMDI) compound as a corrosion inhibitor for galvanized steel through density functional theory. An atomic-scale engineering through the functionalization of PMDI is performed to showcase the enhancement in corrosion inhibition and strengthen the interaction between functionalized PMDI (F-PMDI) and zinc oxide (naturally existing on galvanized steel). PMDI is functionalized with methyl/diamine groups (inh1 (R = −CH 3 , R′ = −CH 3 ), inh2 (R = −CH 3 , R′ = −CH 2 CH 2 NH 2 ), and inh3 (R = −C 6 H 3 (NH 2 ) 2 , R′ = −CH 2 CH 2 NH 2 ). The corrosion inhibition parameters (e.g., orbital energies, electronegativity, dipole moment, global hardness, and electron transfer) indicate the superior corrosion inhibition performance of inh3 (inh3 > inh2 > inh1). Inh3 (∼182.38 kJ/mol) strongly interacts with ZnO(101̅0) compared to inh2 (∼122.56 kJ/mol) and inh1 (∼119.66 kJ/mol). The superior performance of inh3 has been probed through charge density and density of states. Larger available states of N and H (of inh3) interact strongly with Zn and O surf (of the surface), respectively, creating N–Zn and H–O surf bonds. Interestingly, these bonds only appear in inh3. The charge accumulation on O surf , and depletion on H(s), further strengthens the bonding between inh3 and ZnO(101̅0). The microscopic understanding obtained in this study will be useful to develop low-cost and efficient corrosion inhibitors for galvanized steel.

show abstract

“…It should be pointed out that few F-PMDI such as pyridinium-F-PMDI and phosphonium-F-PMDI have been synthesized and widely used in several applications. 50 , 51 …”

Section: Discussionmentioning

confidence: 99%

“…We hope that this work would motivate researchers to synthesize inh3 inhibitors to be applied in industry. It should be pointed out that few F-PMDI such as pyridinium-F-PMDI and phosphonium-F-PMDI have been synthesized and widely used in several applications. , …”

Section: Discussionmentioning

confidence: 99%

Functional Pyromellitic Diimide as a Corrosion Inhibitor for Galvanized Steel: An Atomic-Scale Engineering

et al. 2022

View full text Add to dashboard Cite

show abstract

“… [46] On the other side, the use of pyromellitic diimide motif allows to obtain highly stable chromophoric ylide 24 , which does not show typical Wittig reactivity. Its persistence has been attributed to O:/C: → + P(n O/C → σ* P–C ) interactions indicated by the natural bond orbital calculations [47] …”

Section: Acyclic Organophosphorus Cationic Chromophoresmentioning

confidence: 91%

“… (A) phosphonium dications 22 a and 23 a capable of stepwise reduction, and highly stabilized phosphorus ylide diimine 24 ; (B) normalized absorption spectra of 22 a and 22 b in CHCl 3 solution [42, 45–47] . Adapted from reference [42] with permission from American Chemical Society (2020).…”

Section: Acyclic Organophosphorus Cationic Chromophoresmentioning

confidence: 99%

Cationic Organophosphorus Chromophores: A Diamond in the Rough among Ionic Dyes

Belyaev

Chou

Koshevoy

2020

Chemistry A European J

View full text Add to dashboard Cite

Tunable electron‐accepting properties of the cationic phosphorus center, its geometry and unique preparative chemistry that allows combining this unit with diversity of π‐conjugated motifs, define the appealing photophysical and electrochemical characteristics of organophosphorus ionic chromophores. This Minireview summarizes the achievements in the synthesis of the π‐extended molecules functionalized with P‐cationic fragments, modulation of their properties by means of structural modification, and emphasizes the important effect of cation‐anion interactions, which can drastically change physical behavior of these two‐component systems.

show abstract

“…Subsequently, Cao's group reported the highly-stable phosphonium functionalized PMDI ylide (Figure 1), although their main objective was to synthesize the bis-(phosphonium) functionalized PMDIs similar to the NDI1/NDI2. [51] The synthesis involves dibromo-N, N'-dihexyl pyromellitic diimide as the substrate and PPh 3 as the nucleophile in THF. The single crystal revealed an unexpected phosphonium ylide PMDI3 and not the dicationic species.…”

Section: Pyromellitic Diimides (Pmdi)mentioning

confidence: 99%

Synthesis and Properties of Electron‐Deficient and Electron‐Rich Redox‐Active Ionic π‐Systems

Chorol

Saini

Mukhopadhyay

2022

The Chemical Record

View full text Add to dashboard Cite

There is growing interest towards the design and synthesis of organic redox-active systems, which exist in ionic form. Multi-redox systems entail life-sustaining processes like photosynthesis and cellular respiration. The significant challenge for material scientists is to rationally design complex molecular materials that can store and transfer multiple electrons at low operational potentials and are stable under ambient conditions. Also, important are the designed ionic π-systems that combine efficient electron and ion transport. Here, we discuss the synthesis of ionic π-systems which exist in the closed-shell form. Firstly, different classes of ionic arylenediimides and viologens with different π-linkers are discussed from the synthetic, structural and redox perspective. These ionic π-systems are based on the electron deficient π-scaffolds, and are shown to accumulate upto six electrons. We then discuss electron-rich ionic arylenediimides which can exist in anionic form or zwitterionic form. The anionic electron donors have absorption extending to the near Infrared (NIR) region and can be stabilized in aqueous solution. We also discuss the effect of the electron accumulation on the aromaticity and non-aromaticity of the naphthalene and the imide rings of the naphthalenediimides. We finally discuss in brief, the applications related to the organic mixed ionic-electronic conductors.

show abstract

A Highly Stabilized Phosphonium Ylide that Forms Supramolecular Dimers in Solution and the Solid State

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 7 publications

References 36 publications

Functional Pyromellitic Diimide as a Corrosion Inhibitor for Galvanized Steel: An Atomic-Scale Engineering

Functional Pyromellitic Diimide as a Corrosion Inhibitor for Galvanized Steel: An Atomic-Scale Engineering

Cationic Organophosphorus Chromophores: A Diamond in the Rough among Ionic Dyes

Synthesis and Properties of Electron‐Deficient and Electron‐Rich Redox‐Active Ionic π‐Systems

Contact Info

Product

Resources

About