RESUMEN
14,14'-Bidibenzo[a,j]anthracenes (BDBAs) were prepared by iridium-catalyzed annulation of 5,5'-biterphenylene with alkynes. The molecular geometries of overcrowded BDBAs were verified by X-ray crystallography. The two dibenzo[a,j]anthryl moieties are connected through the sterically hindered 14 positions, resulting in highly distorted molecular halves. The conformation with a small twist angle between two molecular halves can minimize steric conflicts between the substituents at 1 and 13 positions and the carbon atoms of the central axis, as well as steric clashes between those substituents. One such example is octafluoro-substituted BDBA, where the interplanar angle between two anthryl moieties is approximately 31° (currently the lowest reported value, cf. 81° in 9,9'-bianthracene). The intramolecular interactions and electronic couplings between two molecular halves resulted in upfield 1H NMR signals, redshifted absorption and emission bands, and a reduced HOMO-LUMO gap. Photodynamic investigations on BDBAs indicated that the formation of the conventional symmetry-breaking charge transfer (SBCT) state was suspended by restricted rocking around the central C-C bond. Such a mechanism associated with this highly constrained conformation was examined for the first time.
RESUMEN
A new series of biaryls, bi-linear-terphenylenes (BLTPs), were prepared using the tert-butyllithium-mediated cyclization as the key synthetic step. The three-dimensional structures of the studied compounds were verified using X-ray crystallography and DFT calculations. Tetraaryl(ethynyl)-substituted BLTPs are highly crowded molecules, and the internal rotation around the central C-C bond is restricted due to a high barrier (>50â kcal/mol). These structures contain several aryl/terphenylenyl/aryl sandwiches, where the through-space π-π (TSPP) interactions are strongly reflected in the shielding of 1 H NMR chemical shifts, reduction of oxidation potentials, increasing aromaticity of the central six-membered ring and decreasing antiaromaticity of the four-membered rings in a terphenylenyl moiety based on NICS(0) and iso-chemical shielding surfaces. Despite the restricted C-C bond associated intramolecular TSPP interactions for BLTPs in the ground state, to our surprise, the electronic coupling between two linear terphenylenes (LTPs) in BLTPs in the excited state is weak, so that the excited-state behavior is dominated by the corresponding monomeric LTPs. In other words, all BLTPs undergo ultrafast relaxation dynamics via strong exciton-vibration coupling, acting as a blue-light absorber with essentially no emission.
RESUMEN
A series of new [2,2]fluorenophanes has been synthesized and characterized; among them, molecules of crystallographically asymmetric anti-[2.2](1,4)(4,1)fluorenophane (K2C-2) aggregate to form one-dimensional supramolecular chain structures through effective intermolecular π-π overlapping. This, in combination with the synergistic intramolecular π-π interaction, leads to prominent dual emission mediated by charge transfer (CT) exciton delocalization. Support of this new insight is given by mapping the transition density along the π-π packing direction where the intramolecular excitation and intermolecular CT coexist in K2C-2.
RESUMEN
This investigation demonstrates that a series of biphenylenes can be easily prepared from their corresponding halobiphenyls by the cyclization of inâ situ generated 2',3'-didehydro-2-lithiobiphenyls at low temperature. Two remarkable advantages of this synthetic method include 1)â the lack of any need for transition-metal catalysts or reagents in the cyclization, and 2)â the ability to obtain C1-functionalized products by treating the reaction intermediate 1-lithiobiphenylene with an electrophilic reagent. π-Extended derivatives, such as benzobiphenylenes, dibenzobiphenylene, linear/angular [3]phenylenes, and biphenyleno[2,3-b]biphenylenes, were synthesized similarly using suitable biaryls or teraryls.
RESUMEN
A series of diindeno[2,1-b:2',1'-h]biphenylenes with open-shell singlet ground states and interesting properties were prepared. The studied compounds consist of p-quinodimethane moieties, which suffer from geometric perturbation with bond angles of around 90°. The substituent effects on structural parameters, local aromaticity, and properties were systematically explored.