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Synthesis, structural analysis, and properties of highly twisted alkenes 13,13'-bis(dibenzo[a,i]fluorenylidene) and its derivatives.

ABSTRACT: The rotation of a C = C bond in an alkene can be efficiently accelerated by creating the high-strain ground state and stabilizing the transition state of the process. Herein, the synthesis, structures, and properties of several highly twisted alkenes are comprehensively explored. A facile and practical synthetic approach to target molecules is developed. The twist angles and lengths of the central C = C bonds in these molecules are 36-58° and 1.40-1.43 Å, respectively, and confirmed by X-ray crystallography and DFT calculations. A quasi-planar molecular half with the π-extended substituents delivers a shallow rotational barrier (down to 2.35 kcal/mol), indicating that the rotation of the C = C bond is as facile as that of the aryl-aryl bond in 2-flourobiphenyl. Other versatile and unique properties of the studied compounds include a broad photoabsorption range (from 250 up to 1100 nm), a reduced HOMO-LUMO gap (1.26-1.68 eV), and a small singlet-triplet energy gap (3.65-5.68 kcal/mol).

SUBMITTER: Kang HW

PROVIDER: S-EPMC10462764 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Synthesis, structural analysis, and properties of highly twisted alkenes 13,13'-bis(dibenzo[a,i]fluorenylidene) and its derivatives.

Kang Hao-Wen HW Liu Yu-Chiao YC Shao Wei-Kai WK Wei Yu-Chen YC Hsieh Chi-Tien CT Chen Bo-Han BH Lu Chih-Hsuan CH Yang Shang-Da SD Cheng Mu-Jeng MJ Chou Pi-Tai PT Chiang Ming-Hsi MH Wu Yao-Ting YT

Nature communications 20230828 1

The rotation of a C = C bond in an alkene can be efficiently accelerated by creating the high-strain ground state and stabilizing the transition state of the process. Herein, the synthesis, structures, and properties of several highly twisted alkenes are comprehensively explored. A facile and practical synthetic approach to target molecules is developed. The twist angles and lengths of the central C = C bonds in these molecules are 36-58° and 1.40-1.43 Å, respectively, and confirmed by X-ray cry ...[more]

PMID: 37640729

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Project description:Three symmetrical bis-aryl-α,β-unsaturated ketone derivatives, 2,6-di((E)-benzylidene)-cyclohexan-1-one (DBC), 2,6-bis((E)-4-chlorobenzylidene)cyclohexan-1-one (BCC), and (1E,1'E,4E,4'E)-5,5'-(1,4-phenylene)bis(2-methyl-1-phenylpenta-1,4-dien-3-one) (PBMP), have been prepared using the aldol condensation approach toward ketones having two enolizable sites. The structures of DBC, BCC, and PBMP have been resolved via spectrometric methods. Moreover, the crystal structure of PBMP is determined by the single-crystal X-ray diffraction (SC-XRD) technique, which revealed that the PBMP molecular assembly is stabilized by the intermolecular C-H···O bonding and C-O···π and weak T-shaped offset π···π stacking interactions. The Hirshfeld surface analysis (HSA) of the PBMP crystal structure was performed as well, and the results were compared with the results of DBC and BCC. The density functional theory (DFT) study results revealed that the longer conjugated molecule of PBMP has smaller but still quite significant HOMO-LUMO gaps compared to the smaller molecules of BCC and DBC. The natural population analysis (NPA) and natural bonding orbital (NBO) analysis were performed. Accordingly, the hydrogen bonding and dipole-dipole interactions stabilize the crystal structures of these compounds. Additionally, the NBO analysis showed numerous high-energy stabilizing interactions for the PBMP compound due to the presence of numerous delocalized and relatively easily polarizable π-electrons, thus implying its significant thermodynamic stability. According to the global reactivity parameter (GRP) analysis, the compounds BCC and DBC are relatively stable in redox processes and have high thermodynamic stability and relatively lower reactivity in general. The molecular electrostatic potential (MEP) analysis results imply potential formation of the intermolecular hydrogen bonding and dispersion interactions, which stabilizes the crystal structures of these compounds.

Dataset Information

Synthesis, structural analysis, and properties of highly twisted alkenes 13,13'-bis(dibenzo[a,i]fluorenylidene) and its derivatives.

Publications

Synthesis, structural analysis, and properties of highly twisted alkenes 13,13'-bis(dibenzo[a,i]fluorenylidene) and its derivatives.

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