Optical Effect of Varying Acceptors in Pyrene Donor–Acceptor–Donor Chromophores

Keller, Samantha N.; Bromby, Ashley D.; Sutherland, Todd C.

doi:10.1002/ejoc.201700630

Cited by 14 publications

(15 citation statements)

References 22 publications

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“…However, their derivatives are not emissive and thus studies are missing on the influence on the excited state properties and how additional K-region substituents influence 2,7-substituted pyrenes. [40,41] In our previous reports we showed that the influence of a second amine donor at the 2,7-positions on the occupied orbitals is larger than that of a cyano or even Bmes 2 acceptor on the unoccupied orbitals and thus emission from the D-p-D derivative (I, Scheme 2) is further redshifted than the D-p-A compound (II, Scheme 2). Therefore, our initial objective was to utilize two julolidine-like donors at the 2,7-positions and add additional acceptors to the pyrene core to obtain a new class of D-p-A pyrene derivative with unparalleled photophysical properties such as red to NIR emission and interesting redox behavior.…”

Section: Introductionmentioning

confidence: 92%

“…Hence, the electronic coupling V between the localized mixed valence states yields V = 1279 cm À1 for 7 + and I [15] 475 (hexane) 511 (hexane) -À0.18 (CH 2 Cl 2 ) + 0.26 (CH 2 Cl 2 ) 481 (THF) 525 (THF) II [15] 450 (hexane) 464 (hexane) À2.51 (THF) + 0.29 (THF) 462 (THF) 497 (THF) III [32] ---+ 0.14 (CH 2 Cl 2 ) + 0.38 (CH 2 Cl 2 ) IV [28] 453 (toluene) 482 (toluene) ---V [41] 630 (CHCl 3 ) -À0.67 (CHCl 3 ) + 0.39 (CHCl 3 ) -VI [40] 575 (CHCl 3 ) -À1.04 (CHCl 3 ) + 0.33 (CHCl 3 ) -VII [45] 455 (CH 2 Cl 2 ) 538 (CH 2 Cl 2 ) À1.43 (THF) --VIII [46] 435 (CH 2 Cl 2 ) 471 (CH 2 Cl 2 ) --- 2 , which shows that these compounds are class-II compounds, but lie close to the borderline between localized class-II and delocalized class-III compounds, as V is quite large. This result is also in line with the observed broad and asymmetric band shape.…”

Section: Spectroelectrochemistrymentioning

confidence: 99%

“…Sutherland and co‐workers combined the 2,7‐ and 1,8‐positions with the K‐region ( V and VI , Scheme ), respectively, and obtained an S 1 ←S 0 absorbance up to 900 nm, as it was their objective to obtain strongly redshifted absorptions with high molar absorptivities. However, their derivatives are not emissive and thus studies are missing on the influence on the excited state properties and how additional K‐region substituents influence 2,7‐substituted pyrenes …”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Photophysical and Electronic Properties of New Red‐to‐NIR Emitting Donor–Acceptor Pyrene Derivatives

Merz

Dietz

Vonhausen

et al. 2019

Chemistry A European J

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We synthesized new pyrene derivatives with strong bis(para‐methoxyphenyl)amine donors at the 2,7‐positions and n‐azaacene acceptors at the K‐region of pyrene. The compounds possess a strong intramolecular charge transfer, leading to unusual properties such as emission in the red to NIR region (700 nm), which has not been reported before for monomeric pyrenes. Detailed photophysical studies reveal very long intrinsic lifetimes of >100 ns for the new compounds, which is typical for 2,7‐substituted pyrenes but not for K‐region substituted pyrenes. The incorporation of strong donors and acceptors leads to very low reduction and oxidation potentials, and spectroelectrochemical studies show that the compounds are on the borderline between localized Robin‐Day class‐II and delocalized Robin‐Day class‐III species.

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Section: Introductionmentioning

confidence: 92%

Section: Spectroelectrochemistrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Photophysical and Electronic Properties of New Red‐to‐NIR Emitting Donor–Acceptor Pyrene Derivatives

Merz

Dietz

Vonhausen

et al. 2019

Chemistry A European J

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“…The most popular methods for the calculation of dioxothiadiazole properties is standard and involve DFT with B3LYP hybrid functional and a 6-311G++(d,p) or 6-311G++(3df,3pd) basis set. As in the case of most organic molecules, it is fast and reliable in reproducing data for UV-vis and IR interpretation that closely resemble experimental results [ 21 , 42 , 45 , 51 , 59 , 60 ]. For EPR spectra simulations, usually a B98 hybrid functional is used instead.…”

Section: Structure and Geometrymentioning

confidence: 62%

1,2,5-Thiadiazole 1,1-dioxides and Their Radical Anions: Structure, Properties, Reactivity, and Potential Use in the Construction of Functional Molecular Materials

Pakulski

Pinkowicz

2021

Molecules

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This work provides a summary of the preparation, structure, reactivity, physicochemical properties, and main uses of 1,2,5-thiadiazole 1,1-dioxides in chemistry and material sciences. An overview of all currently known structures containing the 1,2,5-thiadiazole 1,1-dioxide motif (including the anions radical species) is provided according to the Cambridge Structural Database search. The analysis of the bond lengths typical for neutral and anion radical species is performed, providing a useful tool for unambiguous assessment of the valence state of the dioxothiadiazole-based compounds based solely on the structural data. Theoretical methodologies used in the literature to describe the dioxothiadiazoles are also shortly discussed, together with the typical ‘fingerprint’ of the dioxothiadiazole ring reported by means of various spectroscopic techniques (NMR, IR, UV-Vis). The second part describes the synthetic strategies leading to 1,2,5-thiadiazole 1,1-dioxides followed by the discussion of their electrochemistry and reactivity including mainly the chemical methods for the successful reduction of dioxothiadiazoles to their anion radical forms and the ability to form coordination compounds. Finally, the magnetic properties of dioxothiadiazole radical anions and the metal complexes involving dioxothiadiazoles as ligands are discussed, including simple alkali metal salts and d-block coordination compounds. The last section is a prospect of other uses of dioxothiadiazole-containing molecules reported in the literature followed by the perspectives and possible future research directions involving these compounds.

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“…Dioxothiadiazole-based electroactive molecules [27][28][29][30][31][32][33] and their complexes [34], on the other hand, are still underrepresented, despite their obvious advantages: easy reduction to a stable radical form, good coordination abilities (including bridging mode) and chemical tunability presented here for the first time. In 2011, Awaga et al studied [1,2,5]thiadiazole [3,4-f][1,10]phenanthroline 1,1-dioxide (L) in context of its electrochemical properties and synthesis of radical salts [35].…”

Section: Introductionmentioning

confidence: 96%

Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties

2019

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Phenanthroline dioxothiadiazoles are redox active molecules that form stable radical anions suitable for the construction of supramolecular magnetic materials. Herein, the preparation, structures and magnetic properties of bis(triphenylphosphine)iminium (PPN) salts of [1,2,5]thiadiazole[3,4-f][1,10]phenanthroline 1,1-dioxide (L), [1,2,5]thiadiazole[3,4-f][4,7]phenanthroline 1,1-dioxide (4,7-L), 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL), and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL) are reported. The preparation of new bromo derivatives of the L: 5-bromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (BrL) and 5,10-dibromo-[1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline 2,2-dioxide (diBrL)—suitable starting materials for further derivatization—are described starting from a commercially available and cheap 1,10-phenanthroline. All PPN salts show antiferromagnetic interactions between the pairs of radical anions, which in the case of PPN(diBrL) are very strong (−116 cm−1; using Ĥ = −2JSS type of exchange coupling Hamiltonian) due to a different crystal packing of the anion radicals as compared to PPN(L), PPN(4,7-L), and PPN(BrL).

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Optical Effect of Varying Acceptors in Pyrene Donor–Acceptor–Donor Chromophores

Cited by 14 publications

References 22 publications

Synthesis, Photophysical and Electronic Properties of New Red‐to‐NIR Emitting Donor–Acceptor Pyrene Derivatives

Synthesis, Photophysical and Electronic Properties of New Red‐to‐NIR Emitting Donor–Acceptor Pyrene Derivatives

1,2,5-Thiadiazole 1,1-dioxides and Their Radical Anions: Structure, Properties, Reactivity, and Potential Use in the Construction of Functional Molecular Materials

Bis(triphenylphosphine)iminium Salts of Dioxothiadiazole Radical Anions: Preparation, Crystal Structures, and Magnetic Properties

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