Synthesis, Structure and Chemistry of a Twisted Olefinic Bis-didentate Proligand: 5,5′-Bi-5H-cyclopenta[2,1-b : 3,4-b′]dipyridinylidene

Riklin, Marianne; Zelewsky, Alex von; Bashall, Alan; McPartlin, Mary; Baysal, Akın; Connor, Joseph A.; Wallis, John D.

doi:10.1002/(sici)1522-2675(19991006)82:10<1666::aid-hlca1666>3.0.co;2-k

Cited by 32 publications

(5 citation statements)

References 21 publications

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“…The lower stability of afOCE3 may be closely related to this small degree of folding. Our calculated results on OCE3 are consistent with the experimental observation that the twisted structure dominates in the condensed phase. − …”

Section: Resultssupporting

confidence: 88%

Quantum Chemical Studies on Electron-Accepting Overcrowded Ethylene with a Polarizable Skeleton

Tada

Fukushima²,

Hada

et al. 2017

J. Phys. Chem. A

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We report the quantum chemical studies on the neutral and radical anion forms of an electron-accepting overcrowded ethylene (OCE1) featuring a highly polarizable skeleton based on the density functional theory (DFT) approach using the M06-2X hybrid functional. Calculated results indicate that OCE1 (bis{4H,8H-4-(dicyanomethylene)benzo[1,2-c:4,5-c']bis[1,2,5]thiadiazol-8-ylidene}) shows conformational behaviors and energetics similar to those of bianthrone (OCE2), a typical thermochromic overcrowded ethylene. Neutral OCE1 and its radical anion have antifolded (afOCE1) and twisted (tOCE1) isomers on their potential energy surfaces. The calculated isomerization barrier heights of OCE1 and its radical anion are considerably low, indicating that its conformation is susceptible to interactions with surrounding molecules. While two afOCE1 molecules can form a simple π-stacked dimer, tOCE1 tends to be converted to afOCE1 when the two tOCE1 molecules come close together, indicating the instability of tOCE1 in the homogeneous OCE1 solid state. The thermochromic behavior difference between OCE1 and OCE2 in solution is closely associated with the considerably small energy difference between the afOCE1 and the tOCE1 as compared with OCE2. The properties of OCE1 are also compared with other typical electron-accepting overcrowded ethylenes in terms of electronic structure, energetics, and conformational behaviors.

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Section: Resultssupporting

confidence: 88%

Quantum Chemical Studies on Electron-Accepting Overcrowded Ethylene with a Polarizable Skeleton

Tada

Fukushima²,

Hada

et al. 2017

J. Phys. Chem. A

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“…However, the structure of the dimer is a twist due to repulsive interactions. − The new class of acceptor showed great potentialities with respect to the previous one as a good overlap with the solar spectrum and optimal average LUMO values. At the present, only one paper takes into account 99′BF derivatives from a computational point of view .…”

Section: Introductionmentioning

confidence: 97%

Theoretical Investigation of the Open Circuit Voltage: P3HT/9,9′-Bisfluorenylidene Derivative Devices

Carlotto

2014

J. Phys. Chem. A

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The calculation of the power conversion efficiency (PCE) value for a bulk heterojunction (BHJ) organic solar cell is complex due to the wide number of parameters involved in the processes. This study focuses the attention on the molecular parameters involved into the open circuit voltage and the PCE definitions and in particular on the electronic coupling and on the lowest unoccupied molecular orbital (LUMO) of the acceptor. A simplified model system composed by a polymer as donor and a novel class of molecules (9,9'-bisfluorenylidene derivatives) as acceptor has been proposed as prototype to simulate the BHJ organic solar cell interface. Several substituents on different positions are tested and the chemical nature/position of substituents have a relevant influence on the electronic coupling and energy level values. Geometrical and electronic properties are obtained using density functional theory (DFT) and time-dependent (TD)-DFT calculations, respectively. A new hypothesis suggests that the minimization of the electronic coupling between the LUMO of the acceptor and the highest occupied molecular orbital (HOMO) of the donor can enhance the PCE reducing the recombination interface processes and calculations showing the possibility to minimize this parameter and fine-tune acceptor energy level through the acceptor functionalization. An accurate balance between electronic coupling and on the LUMO of the acceptor allows to propose the more performing candidate as electron acceptor in a P3HT/99'BF derivative BHJ solar cell.

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“…In the ground state, 9,9'-bifluorenylidene is forced to be coplanar because of the presence of the double bond, but the repulsive interaction between the H1À H1' and H8À H8' protons twists the structure of the dimer. [4,5] In 2001, Agranat et al concluded a series of theoretical study of BAE-containing molecules, to elucidate the dynamic stereochemistry of the BAE skeleton which could contribute towards the development of the molecular materials with interesting properties. [6] In 2010, Wudl et al reported the 9,9'-bifluorenylidene, a typical bistricyclic aromatic ene (BAE) structure, and derivatives as potential electron acceptor for the application of non-fullerene acceptors (see Scheme 1a).…”

Section: Introductionmentioning

confidence: 99%

“…The bistricyclic aromatic ene (BAE) has attracted peoples attentions since 9,9’‐bifluorenylidene was first synthesized in 1875 because of its unique structural characteristic. In the ground state, 9,9’‐bifluorenylidene is forced to be coplanar because of the presence of the double bond, but the repulsive interaction between the H1−H1’ and H8−H8’ protons twists the structure of the dimer [4,5] . In 2001, Agranat et al.…”

Section: Introductionmentioning

confidence: 99%

Fluorenylidene‐Cyclopentadithiophene Based Asymmetric Bistricyclic Aromatic Ene Compounds: Synthesis and Substituents Effects

Xiao

Yang

Chen

et al. 2023

Chemistry A European J

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Low band gap materials have always been a focus of attention due to their potential applications in various fields. In this work, a series of asymmetric bistricyclic aromatic ene (BAE) compounds with fluorenylidene-cyclopentadithiophene (FYT) skeleton were facially synthesized, which were modified with different substituents (À OMe, À SMe). The FYT core exhibit twisted C=C bond with dihedral angles around 30°, and the introduction of À SMe group can provide additional S•••S interaction between molecules, which is conducive to the charge transporting. The UV-Vis spectra, electrochemistry and photoelectron spectroscopy revealed that these compounds have relatively narrow band gaps, particularly, the À SMe modified compounds have slightly lower HOMO and Fermi energy levels than that of the À OMe modified compounds. Furthermore, PSCs devices were fabricated with the three compounds as HTMs, and FYT-DSDPA exhibit the best performance among them, revealing the fine-tuning band structure could influence properties of HTMs.

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Synthesis, Structure and Chemistry of a Twisted Olefinic Bis-didentate Proligand: 5,5′-Bi-5H-cyclopenta[2,1-b : 3,4-b′]dipyridinylidene

Cited by 32 publications

References 21 publications

Quantum Chemical Studies on Electron-Accepting Overcrowded Ethylene with a Polarizable Skeleton

Quantum Chemical Studies on Electron-Accepting Overcrowded Ethylene with a Polarizable Skeleton

Theoretical Investigation of the Open Circuit Voltage: P3HT/9,9′-Bisfluorenylidene Derivative Devices

Fluorenylidene‐Cyclopentadithiophene Based Asymmetric Bistricyclic Aromatic Ene Compounds: Synthesis and Substituents Effects

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