332846-66-9Relevant academic research and scientific papers
Boundaries of anion/naphthalenediimide interactions: From anion-π interactions to anion-induced charge-transfer and electron-transfer phenomena
Guha, Samit,Goodson, Flynt S.,Corson, Lucas J.,Saha, Sourav
supporting information; experimental part, p. 13679 - 13691 (2012/10/08)
The recent emergence of anion-π interactions has added a new dimension to supramolecular chemistry of anions. Yet, after a decade since its inception, actual mechanisms of anion-π interactions remain highly debated. To elicit a complete and accurate understanding of how different anions interact with π-electron-deficient 1,4,5,8-naphthalenediimides (NDIs) under different conditions, we have extensively studied these interactions using powerful experimental techniques. Herein, we demonstrate that, depending on the electron-donating abilities (Lewis basicity) of anions and electron-accepting abilities (π-acidity) of NDIs, modes of anion-NDI interactions vary from extremely weak non-chromogenic anion-π interactions to chromogenic anion-induced charge-transfer (CT) and electron-transfer (ET) phenomena. In aprotic solvents, electron-donating abilities of anions generally follow their Lewis basicity order, whereas π-acidity of NDIs can be fine-tuned by installing different electron-rich and electron-deficient substituents. While strongly Lewis basic anions (OH- and F-) undergo thermal ET with most NDIs, generating NDI?- radical anions and NDI 2- dianions in aprotic solvents, weaker Lewis bases (AcO-, H2PO4-, Cl-, etc.) often require the photoexcitation of moderately π-acidic NDIs to generate the corresponding NDI?- radical anions via photoinduced ET (PET). Poorly Lewis basic I- does not participate in thermal ET or PET with most NDIs (except with strongly π-acidic core-substituted dicyano-NDI) but forms anion/NDI CT or anion-π complexes. We have looked for experimental evidence that could indicate alternative mechanisms, such as a Meisenheimer complex or CH anion hydrogen-bond formation, but none was found to support these possibilities.
Electronically regulated thermally and light-gated electron transfer from anions to naphthalenediimides
Guha, Samit,Goodson, Flynt S.,Roy, Sovan,Corson, Lucas J.,Gravenmier, Curtis A.,Saha, Sourav
body text, p. 15256 - 15259 (2011/11/05)
Anion-induced electron transfer (ET) to π-electron-deficient naphthalenediimides (NDIs) can be channeled through two distinct pathways by adjusting the Lewis basicity of the anion and the π-acidity of the NDI: (1) When the anion and NDI are a strong elect
