Difluoreno[4,3-b:3',4'-d]furan (DFFu) was prepared via a short, scalable, multi-step synthesis, and characterized by crystallography, spectroscopic measurements, and theoretical calculations. Even though the results revealed an open-shell singlet diradical character, DFFu is stable under ambient conditions. The radical cationic and dianionic species of DFFu were also synthesized and characterized.
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http://dx.doi.org/10.1039/d0cc01638a | DOI Listing |
J Comput Chem
January 2025
Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos, Brazil.
In this work, the stability, aromaticity and radical character of pristine and eleven BN-doped armchair 5 and zigzag 5, 6, and 7 periacenes, were chosen for studying the effect of different doping schemes to stabilize the periacene, and to direct the open-shell density into specific regions of the PAH sheets. Ab initio multireference methods and different DFT functionals were used to analyze the singlet triplet (ST) energy. Moreover, a range of descriptors were used to characterize the open-shell character and aromaticity of the different doped structures.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Philipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein-Str. 4, 35032 Marburg, Germany.
Acenes are an important class of polycyclic aromatic hydrocarbons that have gained considerable attention from chemists, physicists, and material scientists, due to their exceptional potential for organic electronics. They serve as an ideal platform for studying the physical and chemical properties of sp carbon frameworks in the one-dimensional limit and also provide a fertile playground to explore magnetism in graphenic nanostructures due to their zigzag edge topology. While higher acenes up to tridecacene have been successfully generated by means of on-surface synthesis, it is imperative to extend their synthesis toward even longer homologues to comprehensively understand the evolution of their electronic ground state.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, DK-5230 Odense M, Denmark.
We present the theory and implementation of a fully variational wave function-density functional theory (DFT) hybrid model, which is applicable to many cases of strong correlation. We denote this model as the multiconfigurational self-consistent on-top pair-density functional theory (MC-srPDFT) model. We have previously shown how the multiconfigurational short-range DFT (MC-srDFT) hybrid model can describe many multiconfigurational cases of any spin symmetry and also state-specific calculations on excited states [Hedegård et al.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Nadia, Mohanpur 741246, WB, India.
In this paper, we demonstrate the performance of several density-based methods in predicting the inversion of S1 and T1 states of a few N-heterocyclic triangulene based fused ring molecules (popularly known as INVEST molecules) with an eye to identify a well performing but cost-effective preliminary screening method. Both conventional linear-response time-dependent density functional theory (LR-TDDFT) and ΔSCF methods (namely maximum overlap method, square-gradient minimization method, and restricted open-shell Kohn-Sham) are considered for excited state computations using exchange-correlation (XC) functionals from different rungs of Jacob's ladder. A well-justified systematism is observed in the performance of the functionals when compared against fully internally contracted multireference configuration interaction singles and doubles and/or equation of motion coupled-cluster singles and doubles (EOM-CCSD), with the most important feature being the capture of spin-polarization in the presence of correlation.
View Article and Find Full Text PDFNat Commun
January 2025
School of Materials Science and Engineering, Hunan University of Science and Technology, Xiangtan, China.
[n]Peri-acenes ([n]PA) have attracted great interest as promising candidates for nanoelectronics and spintronics. However, the synthesis of large [n]PA (n > 4) is extremely challenging due to their intrinsic open-shell radical character and high reactivity. Herein, we report the successful synthesis and isolation of a derivative (1) of peri-hexacene in crystalline form.
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