skip to main content

Title: Synthesis and Characterizations of 5,5′‐Bibenzo[ rst ]pentaphene with Axial Chirality and Symmetry‐Breaking Charge Transfer

Exploration of novel biaryls consisting of two polycyclic aromatic hydrocarbon (PAH) units can be an important strategy toward further developments of organic materials with unique properties. In this study, 5,5′‐bibenzo[rst]pentaphene (BBPP) with two benzo[rst]pentaphene (BPP) units is synthesized in an efficient and versatile approach, and its structure is unambiguously elucidated by X‐ray crystallography. BBPP exhibits axial chirality, and the (M)‐ and (P)‐enantiomers are resolved by chiral high‐performance liquid chromatography and studied by circular dichroism spectroscopy. These enantiomers have a relatively high isomerization barrier of 43.6 kcal mol−1calculated by density functional theory. The monomer BPP and dimer BBPP are characterized by UV‐vis absorption and fluorescence spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. The results indicate that both BPP and BBPP fluoresce from a formally dark S1electronic state that is enabled by Herzberg–Teller intensity borrowing from a neighboring bright S2state. While BPP exhibits a relatively low photoluminescence quantum yield (PLQY), BBPP exhibits a significantly enhanced PLQY due to a greater S2intensity borrowing. Moreover, symmetry‐breaking charge transfer in BBPP is demonstrated by spectroscopic investigations in solvents of different polarity. This suggests high potential for singlet fission in suchπ‐extended biaryls through appropriate molecular design.

more » « less
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Science
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Two water‐soluble zinc(II) phthalocyanines substituted with two or four permethylatedβ‐cyclodextrin (β‐CD) moieties at theαpositions have been utilized as building blocks for the construction of artificial photosynthetic models in water. The hydrophilic and bulkyβ‐CD moieties not only can increase the water solubility of the phthalocyanine core and prevent its stacking in water but can also bind with a tetrasulfonated zinc(II) porphyrin (ZnTPPS) and/or sodium 2‐anthraquinonesulfonate (AQ) in water through host–guest interactions. The binding interactions of these species have been studied spectroscopically, while the photoinduced processes of the resulting complexes have been investigated using steady‐state and time‐resolved spectroscopic methods. In the ternary complexes, the ZnTPPS units serve as light‐harvesting antennas to capture the light energy and transfer it to the phthalocyanine core via efficient excitation energy transfer. The excited phthalocyanine is subsequently quenched by the electron‐deficient AQ units through electron transfer. Femtosecond transient absorption spectroscopy provides clear evidence for the singlet‐singlet energy transfer from the photo‐excited ZnTPPS to the phthalocyanine core with a rate constant (kENT) in the order of 109 s−1. The population of phthalocyanine radical cations indicates the occurrence of electron transfer from the excited phthalocyanine to the AQ moieties, forming a charge‐separated state.

    more » « less
  2. A benzo[ rst ]pentaphene (BPP) substituted by two bis(methoxyphenyl)amino (MeOPA) groups (BPP–MeOPA) was synthesized and clearly characterized by NMR and single-crystal X-ray analysis. Detailed investigations of its photophysical properties, including transient absorption spectroscopy analyses, revealed that the introduction of the MeOPA groups breaks the symmetry of the BPP core, improving its absorption and emission from an S 1 state with both excitonic and charge-transfer character. 
    more » « less
  3. Abstract

    To assess the variability of redox states among mare basalt source regions, investigation of the valence of Ti, Cr, and V and the coordination environment of Ti in pyroxene and olivine in lunar rocks viaXANES(X‐ray absorption near‐edge structure) spectroscopy has been extended to Apollo 17 basalts: two high‐Ti (70017 and 74275) hand samples, and three very low‐Ti (70006,371, 70007,289B, and 70007,296) basalt fragments from the Apollo 17 deep drill core. Valences of Ti in pyroxene of both suites range from 3.6 to 4, or from 40% to 0% Ti3+, averaging 15–20% Ti3+. Assuming Ti3+is more compatible in pyroxene than Ti4+, then even lower Ti3+proportions are indicated for the parental melts. TheVLTpyroxene exhibits a slightly wider range of V valences (2.57–2.96) than the high‐Ti pyroxene (2.65–2.86) and a much wider range of Cr valences (2.32–2.80 versus 2.68–2.86); Cr is generally reduced inVLTpyroxene compared to high‐Ti pyroxene. Valences of Ti and Cr inVLTpyroxene become less reduced with increasing FeO contents, possibly indicating change in oxygen fugacity during crystallization. Olivine in all samples has very low (<20%) proportions of Ti3+, with no Ti3+and higher proportions of Ti in tetrahedral coordination in theVLTs than in the high‐Ti basalts. Olivine in 74275, including that in a dunite clast, has much higher proportions of Cr2+than the pyroxene in that sample, consistent with previous studies indicating that the olivine grains in this sample are xenocrysts and possibly indicating oxidation just prior to pyroxene crystallization. Results for this sample, theVLTs, and previously studied Apollo 14 and 15 basalts all indicate that mare magmas were in reducing environments at depth, as recorded in early crystallization products, and that later, presumably shallower environments, were relatively oxidizing; single, characteristicfO2s of formation cannot be assigned to these samples. A process likely to account for this feature seen in multiple samples is loss by degassing of a reducing, H‐rich vapor (probably H2) during ascent and/or eruption, causing oxidation of the residual melt, recorded in relatively late‐crystallized pyroxene.

    more » « less
  4. Abstract

    Co‐crystallization of the spin‐crossover (SCO) cationic complex, [Fe(1‐bpp)2]2+(1‐bpp=2,6‐bis(pyrazol‐1‐yl)pyridine) with fractionally charged organic anion TCNQδ−(0<δ<1) afforded hybrid materials [Fe(1‐bpp)2](TCNQ)3.5 ⋅ 3.5MeCN (1) and [Fe(1‐bpp)2](TCNQ)4 ⋅ 4DCE (2), where TCNQ=7,7,8,8‐tetracyanoquinodimethane, MeCN=acetonitrile, and DCE=1,2‐dichloroethane. Both materials exhibit semiconducting behavior, with the room‐temperature conductivity values of 1.1×10−4 S/cm and 1.7×10−3 S/cm, respectively. The magnetic behavior of both complexes exhibits strong dependence on the content of the interstitial solvent. Complex1undergoes a gradual temperature‐driven SCO, with the midpoint temperature ofT1/2=234 K. The partial solvent loss by1leads to the increase in theT1/2value while complete desolvation renders the material high‐spin (HS) in the entire studied temperature range. In the case of2, the solvated complex shows a gradual SCO withT1/2=166 K only when covered with a mother liquid, while the facile loss of interstitial solvent, even at room temperature, leads to the HS‐only behavior.

    more » « less
  5. Abstract

    Vanadium multiredox‐based NASICON‐NazV2−yMy(PO4)3(3 ≤z ≤ 4; M = Al3+, Cr3+, and Mn2+) cathodes are particularly attractive for Na‐ion battery applications due to their high Na insertion voltage (>3.5 V vs Na+/Na0), reversible storage capacity (≈150 mA h g−1), and rate performance. However, their practical application is hindered by rapid capacity fade due to bulk structural rearrangements at high potentials involving complex redox and local structural changes. To decouple these factors, a series of Mg2+‐substituted Na3+yV2−yMgy(PO4)3(0 ≤y ≤ 1) cathodes is studied for which the only redox‐active species is vanadium. While X‐ray diffraction (XRD) confirms the formation of solid solutions between they = 0 and 1 end members, X‐ray absorption spectroscopy and solid‐state nuclear magnetic resonance reveal a complex evolution of the local structure upon progressive Mg2+substitution for V3+. Concurrently, the intercalation voltage rises from 3.35 to 3.45 V, due to increasingly more ionic VO bonds, and the sodium (de)intercalation mechanism transitions from a two‐phase fory ≤ 0.5 to a solid solution process fory ≥ 0.5, as confirmed by in operando XRD, while Na‐ion diffusion kinetics follow a nonlinear trend across the compositional series.

    more » « less