Electronic Modulation of Terrylene Diimides Leading to Core‐Twisting, Tunable Emission and Intermolecular Interactions

Abstract

Three new symmetrically para‐phenylethynylene‐substituted terrylene diimide derivatives namely, TDI‐Ph, TDI‐PhCN and TDI‐PhNMe2 were synthesized to study the electronic effects on the structure and properties. The solid‐state single‐crystal structures for TDI‐Ph and TDI‐PhCN as well as for the precursor TDI‐Br4 are presented. The X‐ray diffraction studies revealed twisting in the bay‐area of terrylene core, which improved the solubility as well, despite of having some of the shortest intermolecular Br···Br and C‐H···O interactions in TDI‐Br4. All the compounds exhibited near infra‐red absorption and emission except for TDI‐PhNMe2; especially TDI‐PhNMe2 showed interesting broad absorption ranging from 300 to 970 nm. Further, the effects of electron‐donating and accepting unit on electrochemical and optical properties have been investigated.

Investigation of ion-electrode interactions of linear polyimides and alkali metal ions for next generation alternative-ion batteries

“…The successful synthesis of PTCDA-pPDA using this method presents an advantage over previous syntheses of PDI-based polymers that employ Lewis acids such as Zn(OAc) 2 , 41,42 as it avoids unnecessary metal waste and minimizes potential decarboxylation of the anhydride units by Lewis acids during the polymerization process. 43…”

“…The successful synthesis of PTCDA-pPDA using this method presents an advantage over previous syntheses of PDIbased polymers that employ Lewis acids such as Zn(OAc) 2 , 41,42 as it avoids unnecessary metal waste and minimizes potential decarboxylation of the anhydride units by Lewis acids during the polymerization process. 43 Aer synthesis, the polymers were integrated into battery electrodes by mixing 60% active material, 30% Super P carbon, and 10% polyvinylidene uoride (PVDF) binder by weight. The electrodes were assembled as cathodes into 2032 coin cells using Li, Na, or K metal as the anodes accompanied by the corresponding electrolyte solutions (LiPF 6 , NaPF 6 , or KPF 6 , respectively) in ethylene carbonate (EC):diethyl carbonate (DEC) (1 : 1 by vol).…”

Isolation and Structural Characterization of Regioisomers of Dibrominated Terrylene Diimides

“…Terrylene diimide (TDI), an extended member of the rylene diimide (RDI) family, is gaining attention due to its NIR absorption and emission behavior . TDI inherits the outstanding photochemical, thermal, and chemical stabilities, high molar absorption coefficients, and near-unity fluorescence quantum yield from its shorter homologues. − Collectively, these attributes make these molecules versatile platforms for modern optoelectronic applications . Although TDI was first synthesized by Müllen et al in 1997, it remains comparatively less explored due to synthetic challenges and solubility issues associated with its extended planar π-surface. , Similar to the case of shorter RDIs, functionalizing the TDI core by either an electron-donating or an electron-withdrawing group solves the solubility issue, while also influencing the optical and electronic properties. , However, the main attraction towards TDI stems from the fact that the additional naphthalene unit present offers more flexibility for diverse functionalization of the core .…”