Study on Facile Synthesis, Crystal Structure, and Solid-State Fluorescence of Dicyclohexane-Annelated Anthracene

Abstract

Dicyclohexane-annelated anthracene was synthesized by a new efficient method, which employed the Diels–Alder reaction between in situ-generated 2,3-dehydronaphthalene and dicyclohexane-fused furan. The molecule adopted antiparallel face-to-face slipped π-stacking in its crystal structure, which induced an excimer-like emission in the solid state.

The Diels–Alder Reaction for the Synthesis of Polycyclic Aromatic Compounds

“…A mixture of stereomers was hydrogenated without separation in the presence of a catalyst with further dehydration and the formation of 1,4,5,8‐tetraalkyl anthracenes 200a‐d . The applicability of the described synthetic approach to the preparation of asymmetric cyclohexane‐fused anthracene was demonstrated by the same research group a year later (Scheme ) . The hydrogenation‐dehydration sequence for compound 203 turned out to be inapplicable due to the steric hindrance of the carbon–carbon double bond; therefore, one‐step deoxygenation with low‐valent titanium was performed with 66 % yield.…”

Tuning the Solid‐State Optical Properties of Tetracene Derivatives by Modification of the Alkyl Side‐Chains: Crystallochromy and the Highest Fluorescence Quantum Yield in Acenes Larger than Anthracene

“…[22] We also investigated the fluorescence properties of several alkyl‐substituted anthracenes ( 18 – 23 ) and found that some of these derivatives exhibited high quantum yields in the solid state (Table 1). [23] However, there were few reports of the solid‐state fluorescence of acenes larger than anthracene. Therefore, we examined the fluorescence of alkyl‐substituted tetracenes in parallel with our previously mentioned examination of solid‐state color.…”

“… [a], [b], [c], [d] [a] Excited at 325 nm; [b] absolute quantum yield in its powdered form, measured with an integrating sphere; [c] see Ref. [23a]; [d] see Ref. [23b].…”

1,4,7,10‐Tetraisoalkyltetracenes: Tuning of Solid‐State Optical Properties and Fluorescence Quantum Yields by Peripheral Modulation

“…Organic materials exhibiting highly intense emissions in the solid state have recently received considerable interest because molecules with high absolute quantum yields are quite limited. [5][6][7][8][9][10][11][12][13][14] Although several approaches, such as substituent protection, [5] π-π stacking protection, [6][7][8] intramolecular chargetransfer transition, [9] aggregation-induced emission, [10,11] and modulating molecular arrangements, [12][13][14] have been reported, molecular design to control solid-state fluorescence is not fully understood. To develop new tetracenes with high emission efficiencies, we thought to introduce isoalkyl groups as branched alkyl side-chains instead of linear alkyl groups.…”