Naphtho[1,2‐b:5,6‐b′]dithiophene Building Blocks and their Complexation with Cyclobis(paraquat‐p‐phenylene)

Jensen, Michael Hansen; Olsen, Gunnar; Kristensen, Rikke Holmslykke; Takimiya, Kazuo; Jeppesen, Jan O.

doi:10.1002/ejoc.201901161

Cited by 4 publications

(3 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The protons associated with the numerous different SC H 3 groups attached to the TTF and MPTTF units were all observed to be shifted downfield from δ =2.30–2.70 ppm in the unoxidized 1 4+ to δ =2.85–3.05 ppm in the oxidized sample of 1 4+ . Previous investigations have shown that this behavior is entirely consistent with formation of the TTF 2+ and MPTTF 2+ dications, and therefore, of the tetra‐oxidized [2]rotaxane 1 8+ . Likewise, the protons associated with the MPTTF 2+ unit (i.e., the pyrrole‐ H protons) are shifted downfield ( δ =8.07 and 7.99 ppm in 1 8+ , Figure S2) compared to unoxidized 1 4+ ( δ =6.17–6.61 ppm), an observation that is completely consistent with the formation of a non‐complexed MPTTF 2+ dication.…”

Section: Resultssupporting

confidence: 77%

“…Previous investigations [12b, 29] have shown that this behavior is entirely consistent with formationo ft he TTF 2 + and MPTTF 2 + dications, and therefore, of the tetra-oxidized [2]rotaxane 1 8 + . [30] Likewise, the protons associatedw ith the MPTTF 2 + unit (i.e.,t he pyrrole-H protons) are shiftedd ownfield (d = 8.07 and 7.99 ppm in 1 8 + ,F igure S2) comparedt ou noxidized 1 4 + (d = 6.17-6.61 ppm), an observation that is completely consistent with the formation of an on-complexed MPTTF 2 + dication.…”

Section: Chemical Oxidation Of 1 4 + +mentioning

confidence: 99%

See 1 more Smart Citation

Probing the Electrostatic Barrier of Tetrathiafulvalene Dications using a Tetra‐stable Donor–Acceptor [2]Rotaxane

Jensen

Kristensen

Andersen

et al. 2020

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

At etra-stable donor-acceptor [2]rotaxane 1·4PF 6 has been synthesized. The dumbbell component is comprised of an oxyphenylene (OP), at etrathiafulvalene (TTF), a monopyrrolo-TTF (MPTTF), and ah ydroquinone (HQ) unit, which can act as recognition sites (stations) for the tetra-cationic cyclophane cyclobis(paraquat-p-phenylene) (CBPQT 4 + ). The TTF and the MPTTF stations are located in the middle of the dumbbell component and are connected by at riethylene glycol (TEG) chain in such aw ay that the pyrrole moiety of the MPTTFs tation points towardt he TTF station, while the TTF and MPTTFs tations are flankedb yt he OP and HQ stations on their left hand side and right hand side, respectively.T he [2]rotaxane was characterized in solution by 1 HNMR spectroscopy and cyclic voltammetry.T he spectroscopic data revealed that the majority (77 %) of the tetrastable [2]rotaxane 1 4 + exist as the translational isomer 1·MPTTF 4 + in which the CBPQT 4 + ring encircles the MPTTF station.T he electrochemical studiess howedt hat CBPQT 4 + in 1·MPTTF 4 + undergoes ring translation as result of electrostatic repulsion from the oxidized MPTTFu nit. Following tetra-oxidation of 1·MPTTF 4 + ,ahigh-energy state of 1 8 + was obtained (i.e., 1·TEG 8 + )i nwhich the CBPQT 4 + ring waslocated on the TEGl inker connecting the di-oxidized TTF 2 + and MPTTF 2 + units. 1 HNMR spectroscopy carriedo ut in CD 3 CN at 298 Ko nac hemically oxidized sample of 1·MPTTF 4 + revealed that the metastable state 1·TEG 8 + is only short-lived with al ifetime of af ew minutes and it was found that 70 % of the positivelyc harged CBPQT 4 + ring movedf rom 1·TEG 8 + to the HQ station,w hile 30 %m oved to the much weaker OP station. These resultsc learly demonstrate that the CBPQT 4 + ring can cross both an MPTTF 2 + and aT TF 2 + electrostatic barriera nd that the free energy of activation required to cross MPTTF 2 + is ca. 0.5 kcal mol À1 smaller as compared to TTF 2 + .[a] Dr.Scheme2.Synthesis of the dumbbell 8 and the tetra-stable [2]rotaxane 1·4PF 6 together with cartoon representations of the three different translational isomers 1·4PF 6 ·TTF, 1·4PF 6 ·MPTTF, and 1·4PF 6 ·HQ present in solution.N otethat compounds 1·4PF 6 , 2, 4,and 8 all exist as amixture of E and Z isomers.

show abstract

Section: Resultssupporting

confidence: 77%

Section: Chemical Oxidation Of 1 4 + +mentioning

confidence: 99%

Probing the Electrostatic Barrier of Tetrathiafulvalene Dications using a Tetra‐stable Donor–Acceptor [2]Rotaxane

Jensen

Kristensen

Andersen

et al. 2020

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…The two solvent choices present distinctively different molecular environments to compare crystallization within a theoretical framework: Toluene can be viewed as an effective (good) solvent given favorable noncovalent intermolecular interactions among the aromatic cores of toluene and NDT, while hexane can be viewed as a nonfavorable (poor) solvent given the aliphatic nature of the solvent that may introduce an additional driving force for phase separation. 11 We note that toluene has been used to dissolve NDT-based crystals, 48 whereas hexane has been used as a recrystallization solvent to grow NDT crystals. 46…”

Section: ■ Introductionmentioning

confidence: 99%

Atomistic Perspective of the Crystallization of Naphthodithiophene in Two Hydrocarbon Solvents

Karunasena,

Bjelobrk,

Risko

2023

Chem. Mater.

View full text Add to dashboard Cite

A priori control over crystallization, whether one attempts to induce or prevent crystallization, is critical across many areas of materials chemistry. The capacity to regulate crystallization in solution requires a comprehensive understanding of the deceivingly simple interrelationships among the chemical compositions and structures of the solute and solvent and external environmental parameters such as temperature and pressure. While there have been tremendous advances in crystal structure prediction based solely on chemical composition and molecular structure, there remains insufficient knowledge, especially at the atomic scale, to regulate crystallinity with precision during solution processing. Here, we make use of the constant chemical potential molecular dynamics (CμMD) algorithm to explore the growth of naptho[1,2-b:5,6-b′]dithiophene (NDT), a molecule with structural anisotropy and no specific chemical / noncovalent intermolecular interaction directors (e.g., no hydrogen bonding or pendant functional groups) that packs in the commonly found herringbone (two-dimensional layer) packing motif. We demonstrate at the atomic scale how variations in NDT (solute) concentration, solvent, and temperature impact both the initiation of crystal formation (nucleation) and the propagation of crystals (growth) along different crystallographic directions. In total, this investigation reveals atomic-scale thermodynamic and kinetic details important to crystallization that can be exploited to control the processing of organic materials.

show abstract

Solvent efficiency and role of dispersion and electrostatic forces for chiral discrimination of sulfur-containing amino acids by tetra-protonated CBPQT macrocycle

Sajid,

Mahmood,

Sohaib

et al. 2024

Journal of Molecular Liquids

View full text Add to dashboard Cite

Naphtho[1,2‐b:5,6‐b′]dithiophene Building Blocks and their Complexation with Cyclobis(paraquat‐p‐phenylene)

Cited by 4 publications

References 73 publications

Probing the Electrostatic Barrier of Tetrathiafulvalene Dications using a Tetra‐stable Donor–Acceptor [2]Rotaxane

Probing the Electrostatic Barrier of Tetrathiafulvalene Dications using a Tetra‐stable Donor–Acceptor [2]Rotaxane

Atomistic Perspective of the Crystallization of Naphthodithiophene in Two Hydrocarbon Solvents

Solvent efficiency and role of dispersion and electrostatic forces for chiral discrimination of sulfur-containing amino acids by tetra-protonated CBPQT macrocycle

Contact Info

Product

Resources

About