Tunable electronic interactions between anions and perylenediimide

Abstract

Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF. These interactions have been fully characterized by UV/Vis, NMR, and EPR spectroscopies. These results demonstrate the generality of anion-induced ET events in aprotic solvents and further refute a notion that strong Lewis basic hydroxide and fluoride ions can only trigger nucleophilic attack to form covalent bonds instead of acting as sacrificial electron donors to π-acids under appropriate conditions.

Pyridalthiadiazole acceptor-functionalized triarylboranes with multi-responsive optoelectronic characteristics

“…Saha and coworkers showed that addition of strongly Lewis basic anions to electron-deficient naphthalene diimides (NPI) leads to anion–π interactions that ultimately result in reduction and generation of the corresponding [NPI]˙ – radical anions. 18 It seems plausible then that in the case of BDT-PT and BDT-2PT , where anion binding to boron is sterically hindered by the very bulky substituent, reduction of the compounds by F – effectively competes with the anion binding to boron. This process would be less favorable when using [Bu 4 N][Ph 3 SiF 2 ] as the F – source due to the diminished reducing power of the fluorosilicate complex.…”

Spin–Orbit Charge‐Transfer Intersystem Crossing in Anthracene–Perylenebisimide Compact Electron Donor–Acceptor Dyads and Triads and Photochemical Dianion Formation

“…On photoirradiation by unfiltered white light of ax enon lamp in the presenceo fT EOA, the absorption bandso fPBI-9-An at 512 nm decreased, and new absorptionb ands centered at 708, 802, 864, and 954 nm appeared and intensified, which are the characteristicD 0 !D n absorption of PBIC À À . [91][92][93] Notably, the absorption band centered at 369 nm (AN absorption) do not change, that is, the AN moiety remains intact during photoreduction. This implies that PBIC À À is formed,d ue to photoreductionofthe dyad in the presence of TEOA.…”

Tuning Intramolecular Charge Transfer through Adjusting Hydrogen Bonding by Anions

“…In the presence of BPPN‐2OH , the signal for the F − anions shifted upfield from −113 to −127 ppm (Figure S10), consistent with shielding of F − ions by the PBI core and the biphenyl group. In addition, a broad singlet appeared at −153 ppm, representing HF 2 − anions . In the 19 F NMR spectra, the lack of any other new signals for F − species ruled out the possibility of covalent C−F bond formation through nucleophilic attack of an F − anion on the PBI core.…”