Supramolecular ultrafast energy and electron transfer in a directly linked BODIPY–oxoporphyrinogen dyad upon fluoride ion binding

Abstract

Photosynthetic mimicry of sequential ultrafast energy transfer followed by electron transfer upon fluoride binding to the oxoporphyrinogen cavity in a BODIPY–oxoporphyrinogen dyad is demonstrated.

Does Location of BF2-Chelated Dipyrromethene (BODIPY) Ring Functionalization Affect Spectral and Electron Transfer Properties? Studies on α-, β-, and Meso-Functionalized BODIPY-Derived Donor–Acceptor Dyads and Triads

“…In recent years, our groups have explored various antenna−donor−acceptor model compounds possessing BODIPY as one of the active components. [18][19][20][21][22][23][24][25][26]37,38 In the majority of the studies where BODIPY formed part of the donor−acceptor system, the functionalization was carried out at the meso-position. 18−26,29−36 Only a handful of studies utilized the pyrrole α and β positions.…”

“…Establishing structure–function relations in light-induced charge separation processes in synthetic donor–acceptor conjugates is not only important to further our understanding of natural photosynthesis , but also vital for solar energy harvesting and building optoelectronic devices. − In this context, harvesting sunlight into chemical energy by an artificial photosynthetic approach is considered one of the possible solutions to fulfill the ever increasing global energy needs without significantly affecting the environment. , For this, a wide variety of artificial photosynthetic donor–acceptor conjugates have been designed and synthesized; some of these systems have shown to be capable of both wide-band capture of solar photons and the ability to use the absorbed energy to generate charge-separated states of appreciable energy. − Using elegant synthetic chemistry, it has been possible to fine-tune the light capture and conversion efficiency to a desired value by altering the D/A units, their relative distance, and the π-linker connecting them. − …”

“…BF 2 -chelated dipyrromethenes (BODIPYs) (see Figure for the structure) have gained much attention in recent years as building blocks of artificial photosynthetic systems, sensors, and probes. − BODIPYs exhibit high absorption coefficients, high fluorescence quantum yields, and tunable redox potentials. − Their electronic and photonic properties can be tuned by a proper choice of electron rich/deficient addends and by performing substitution at different positions of the BODIPY macrocycle. − These features have made BODIPY an attractive fluorophore as its absorption can be extended over a wide spectral range. In recent years, our groups have explored various antenna–donor–acceptor model compounds possessing BODIPY as one of the active components. − ,, In the majority of the studies where BODIPY formed part of the donor–acceptor system, the functionalization was carried out at the meso-position. − ,− Only a handful of studies utilized the pyrrole α and β positions. − Importantly, although substitution effect on absorption and fluorescence properties as a function of different locations of the BODIPY ring has been studied, no systematic study has been reported on the substitution effects of different locations on the BODIPY ring on their electron transfer properties. In the present study, we have undertaken a task where BODIPY has been functionalized at the meso-, α-, and β-pyrrole positions to visualize its effects on the spectral and electrochemical properties with acetylene ( 1–3 in Figure ) and bis-acetylene ( 4–6 ) π-extenders.…”

Singlet Fission from Upper Excited States of Bodipy Crystalline Film and Single Crystal

“…Moreover, a rise time of 15 ps was also obtained in ESA, and it can be attributed to intramolecular vibrational relaxation (IVR); the solvation process cannot be fully ruled out as well. 46 There is a strong negative band at 440−600 nm with a maximum of 500 nm which is the superposition of the ground state bleaching (GSB) and stimulated emission (SE); GSB and SE exhibit the same lifetimes as ESA.…”

Estimation of Enantiomeric Excess Based on Rapid Host–Guest Exchange

“…Oxoporphyrinogens (OxP, 5,10,15,20-tetrakis(3,5-di-t-butyl-4-oxocyclohexa-2,5-dien ylidene)porphyrinogen [48,49]) derived from the 2-electron oxidation of 5,10,15,20-tetrakis(3,5-dit-butyl-4-hydroxyphenyl)porphyrin [50] are a class of tetrapyrroles related to, but apart from, the calix [4]pyrroles [51]. They have been studied for their interactions with anions [52], anion-cation pairs [53], water [54], and other analytes [55][56][57] as components of multichromophore systems as an electron acceptor [58][59][60][61][62], and also as H-bonding catalysts [63]. Their saddle-like structures allow for hydrogen bonding interactions with a wide variety of potential analytes, which can also lead to changes in the electronic absorption spectra of the chromophore incorporated in the macrocyclic framework.…”