Hexasubstituted Benzenes with Ultrastrong Dipole Moments

Wudarczyk, Jakob; Papamokos, George; Margaritis, Vasilis; Schollmeyer, Dieter; Hinkel, Felix; Baumgarten, Martin; Floudas, George; Müllen, Kläus

doi:10.1002/anie.201508249

Cited by 76 publications

(63 citation statements)

References 34 publications

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“…In the crystal lattice of Ag-H4,t here are two independent structures (Ag (1) -H4 and Ag (2) -H4). [8] . [12f] As inferred from the specific angles of Figure 1.…”

Section: Resultsmentioning

confidence: 75%

Organometallic Group 11 (Cu^III, Ag^III, Au^III) Complexes of a trans‐Doubly N‐Confused Porphyrin: An “Expanded Imidazole” Structural Motif

Yan

Yang

Ishida

et al. 2017

Chemistry A European J

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Complexation of group 11 metal cations with an α-bis(phenylthio)-substituted trans-doubly N-confused porphyrin (trans-N CP : 4) afforded a series of square-planar trivalent organometallic complexes (i.e., Cu-H4, Ag-H4, and Au-H4). The X-ray crystal structures of the complexes revealed highly planar core geometries along with the presence of peripheral amine and imine nitrogen sites of the pyrrolic moieties. NMR, UV/Vis absorption, and magnetic circular dichroism (MCD) spectroscopies suggested the 18 π-electron aromaticity of the complexes. The aromaticity was also fully analyzed by various theoretical methodologies such as nucleus-independent chemical shift (NICS) and anisotropic induced current density (ACID) calculations. The central metal affects the amphiprotic character of the complexes possessing both pyrrolic amino nitrogen and imino nitrogen atoms at the periphery, which was examined by the photometric titration with trifluoroacetic acid (TFA) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), respectively. The inherent acidity of the complexes was followed in the order; Cu-H4>Au-H4>Ag-H4 and that of basicity was Au-H4>Ag-H4>Cu-H4. The complexes could be considered as an "expanded imidazole" structural motif.

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“…In the crystal lattice of Ag-H4,t here are two independent structures (Ag (1) -H4 and Ag (2) -H4). [8] . [12f] As inferred from the specific angles of Figure 1.…”

Section: Resultsmentioning

confidence: 75%

Organometallic Group 11 (Cu^III, Ag^III, Au^III) Complexes of a trans‐Doubly N‐Confused Porphyrin: An “Expanded Imidazole” Structural Motif

Yan

Yang

Ishida

et al. 2017

Chemistry A European J

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“…4). A molecular dipole moment for compound 4c was calculated at 3.1 D and can be compared for example to 1,2,4,5-tetrafluorocyclohexane ( 2 , 5.2 D) [18]. …”

Section: Resultsmentioning

confidence: 99%

“…The search for new and more diverse polar hydrophobic scaffolds is attractive for drug discovery research and new materials [18]. In our own lab we have been exploring the synthesis and properties of differently fluorinated aliphatic structures based on the cyclopentane ( 1 ) and cyclohexane ( 2 and 3 ) rings, compounds which can show quite large dipole moments depending on the stereochemistry [19–20] (Fig.…”

Section: Introductionmentioning

confidence: 99%

Organofluorine chemistry: Difluoromethylene motifs spaced 1,3 to each other imparts facial polarity to a cyclohexane ring

Jones¹,

Callejo²,

Slawin³

et al. 2016

Beilstein J. Org. Chem.

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2,2-Dimethyl-5-phenyl-1,1,3,3-tetrafluororocyclohexane has been prepared and characterised as an example of a facially polarised cyclohexane containing 1,3 related CF2 groups. The dipolar nature of the ring arises from the axial orientation of two of the C–F bonds pointing in the same direction, and set by the chair conformation of the cyclohexane. This electrostatic profile is revealed experimentally both in the solid-state (X-ray) packing of the rings and by solution (NMR) in different solvents. A computationally derived electrostatic profile of this compound is consistent with a more electronegative and a more electropositive face of the cyclohexane ring. This placing of CF2 groups 1,3 to each other in a cyclohexane ring is introduced as a new design strategy which could be applicable to the preparation of polar hydrophobic cyclohexane motifs.

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“…[21] Among the polymer acceptors in this study, PNDITCVT-R showed the highest Δµ ge of 23.53 D, with large dipole moments in both the ground and excited states of 4.31 and 26.21 D, respectively. [22] With these large Δµ ge values of PNDITCVT-R, more polarized excitons can be produced and the electron-hole separation distance increased, resulting in reduced exciton binding energy. The higher Δµ ge values are attributed mainly to the asymmetric chemical structure of TCVT and the presence of the electronwithdrawing cyano groups.…”

Section: Dipole Moment Change (δµ Ge )mentioning

confidence: 99%

Design of Cyanovinylene‐Containing Polymer Acceptors with Large Dipole Moment Change for Efficient Charge Generation in High‐Performance All‐Polymer Solar Cells

Cho

Kim

et al. 2017

Advanced Energy Materials

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over fullerene-based PSCs, including easily tunable polymer properties, simultaneous light absorption by both donors and acceptors, and enhanced stability against mechanical and thermal stresses. [1] However, few all-PSCs have been reported to exhibit power conversion efficiencies (PCEs) higher than 7%, as many systems have relatively low short-circuit current densities (J SC ) and fill factors (FF). [1d,e,2] The low performance of all-PSCs is mainly attributed to (i) low electron mobility of polymer acceptors within the photoactive layer and (ii) inefficient exciton dissociation at donor/acceptor (D/A) interfaces as a result of the anisotropic packing structure of donor and acceptor polymers. [3] Another hurdle for efficient exciton dissociation is lower dielectric constant of the polymers than that of fullerene derivatives, which increases the binding energy of the excitons in all-PSCs. [4] To develop polymer acceptors with high electron mobility, various n-type polymers have been designed and synthesized, among which naphthalenediimide (NDI)-based copolymers have attracted great attention due to strong π-π interactions between NDI units and facile functionalization through the N-position of NDI moiety. [1b,c,2a,c,5] However, lowest unoccupied molecular orbital (LUMO) of NDI-based polymers is often largely localized on the NDI units due to the high electron affinity of NDI, which hinders efficient intermolecular electron transport. [5n,6] Thus, insertion of strong electron-withdrawing groups into the electron donating moieties of the NDI-based copolymers would be a promising approach to enhance electron transport and intermolecular interactions by delocalizing the LUMO over the polymer backbone and generating stronger orbital overlaps between the adjacent polymer chains. [6a,b] Charge generation at the interfaces of the D/A polymer domains within the photoactive layer depends significantly on the interfacial dipole moment between the donor and acceptor and the internal dipole moment of the polymers. [3a,5l,7] Additionally, for conjugated polymers with a large dipole moment difference between the ground and excited states (Δµ ge ), the electron-hole separation distance within the polymer chain increases as the polarized exciton is formed, which reduces the Designing polymers that facilitate exciton dissociation and charge transport is critical for the production of highly efficient all-polymer solar cells (all-PSCs). Here, the development of a new class of high-performance naphthalenediimide (NDI)-based polymers with large dipole moment change (Δµ ge ) and delocalized lowest unoccupied molecular orbital (LUMO) as electron acceptors for all-PSCs is reported. A series of NDI-based copolymers incorporating electron-withdrawing cyanovinylene groups into the backbone (PNDITCVT-R) is designed and synthesized with 2-hexyldecyl (R = HD) and2-octyldodecyl (R = OD) side chains. Density functional theory calculations reveal an enhancement in Δµ ge and delocalization of the LUMO upon the incorporation of cyano...

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Hexasubstituted Benzenes with Ultrastrong Dipole Moments

Cited by 76 publications

References 34 publications

Organometallic Group 11 (Cu^III, Ag^III, Au^III) Complexes of a trans‐Doubly N‐Confused Porphyrin: An “Expanded Imidazole” Structural Motif

Organometallic Group 11 (Cu^III, Ag^III, Au^III) Complexes of a trans‐Doubly N‐Confused Porphyrin: An “Expanded Imidazole” Structural Motif

Organofluorine chemistry: Difluoromethylene motifs spaced 1,3 to each other imparts facial polarity to a cyclohexane ring

Design of Cyanovinylene‐Containing Polymer Acceptors with Large Dipole Moment Change for Efficient Charge Generation in High‐Performance All‐Polymer Solar Cells

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Hexasubstituted Benzenes with Ultrastrong Dipole Moments

Cited by 76 publications

References 34 publications

Organometallic Group 11 (CuIII, AgIII, AuIII) Complexes of a trans‐Doubly N‐Confused Porphyrin: An “Expanded Imidazole” Structural Motif

Organometallic Group 11 (CuIII, AgIII, AuIII) Complexes of a trans‐Doubly N‐Confused Porphyrin: An “Expanded Imidazole” Structural Motif

Organofluorine chemistry: Difluoromethylene motifs spaced 1,3 to each other imparts facial polarity to a cyclohexane ring

Design of Cyanovinylene‐Containing Polymer Acceptors with Large Dipole Moment Change for Efficient Charge Generation in High‐Performance All‐Polymer Solar Cells

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Organometallic Group 11 (Cu^III, Ag^III, Au^III) Complexes of a trans‐Doubly N‐Confused Porphyrin: An “Expanded Imidazole” Structural Motif

Organometallic Group 11 (Cu^III, Ag^III, Au^III) Complexes of a trans‐Doubly N‐Confused Porphyrin: An “Expanded Imidazole” Structural Motif