The construction and precise control of the face-to-face π-stacked arrangements of anthracene fluorophores in the crystalline state led to a remarkable red shift in the fluorescence spectrum due to unprecedented excited oligomer formation. The arrangements were regulated by using organic salts including anthracene-1,5-disulfonic acid (1,5-ADS) and a variety of aliphatic amines. Because of the smaller number of hydrogen atoms at the edge positions and the steric effect of the sulfonate groups, 1,5-ADS should prefer face-to-face π-stacked arrangements over the usual edge-to-face herringbone arrangement. Indeed, as the alkyl substituents were lengthened, the organic salts altered their anthracene arrangement to give two-dimensional (2D) edge-to-face and end-to-face herringbone arrangements, one-dimensional (1D) face-to-face zigzag and slipped stacking arrangements, a lateral 1D face-to-face arrangement like part of a brick wall, and a discrete monomer arrangement. The monomer arrangement behaved as a dilute solution even in the close-packed solid state to emit deep blue light. The 1D face-to-face zigzag and slipped stacking of the anthracene fluorophores caused a red shift of 30-40 nm in the fluorescence emission with respect to the discrete arrangement, probably owing to ground-state associations. On the other hand, the 2D end-to-face stacking induced a larger red shift of 60 nm, which is attributed to the excimer fluorescence. Surprisingly, the brick-like lateral face-to-face arrangement afforded a remarkable red shift of 150 nm to give yellow fluorescence. This anomalous red shift is probably due to excited oligomer formation in such a lateral 1D arrangement according to the long fluorescence lifetime and little shift in the excitation spectrum. The regulation of the π-stacked arrangement of anthracene fluorophores enabled the wide modulation of the fluorescence and a detailed investigation of the relationships between the photophysical properties and the arrangements.

Solid-state excimer emission of anthracene and its derivatives is a rare case at ambient conditions. We have designed organic salts composed of 9,10-bis(4-aminophenyl)anthracene (BAPA) and mineral acids in order to regulate the anthracene arrangement for investigation of the plausible geometry. From fluorescence measurement of three BAPA salts (nitrate: salt 1, chloride: salt 2, phosphate: salt 3), emission colors were changed by the effect of the mineral acids on the crystal structure. Notably, salt 3 crystal exhibited a bluish-green color derived from excimer emission at ambient conditions. On the basis of X-ray crystallographic analysis, the excimer emission of the salt 3 crystal was attributed to a tilt–slide type of anthracene geometry. In the geometry, π-planes of the anthracene moieties partially overlapped next to each other, an angle between the π-planes is 44°, and the nearest C–C distance is 3.7 Å. Such molecular geometry of partial overlapping of the anthracene rings and slightly longer C–C distance than that of common active π–π interaction (3.4–3.5 Å) was constructed of OH···O hydrogen bonds among mineral acid ions. These results suggest that the hydrogen bonds among mineral acid ions lead to the proximity of BAPA, following the excimer emission.

Organic-inorganic hybrid salts based on 1,5-bisaminophenylanthracene were able to overcome aggregation-induced quenching and emit multiple colours of luminescence according to the counter acid employed. Moreover, the emission colour could be reversibly and dynamically changed on absorption and desorption of guest molecules.

A host framework for inclusion of various guest molecules was investigated by preparation of inclusion crystals of 1,8-bis(4-aminophenyl)anthracene (1,8-BAPA) with organic solvents. X-ray crystallographic analysis revealed construction of the same inclusion space incorporating 1,8-BAPA and eight guest molecules including both non-polar (benzene) and polar guests (N,N-dimethylformamide, DMF). Fluorescence efficiencies varied depending on guest molecule polarity; DMF inclusion crystals exhibited the highest fluorescence intensity (ΦF=0.40), four times as high as that of a benzene inclusion crystal (ΦF=0.10). According to systematic investigations of inclusion phenomena, strong host–guest interactions and filling of the inclusion space led to a high fluorescence intensity. Temperature-dependent fluorescence spectral measurements revealed these factors effectively immobilised the host framework. Although hydrogen bonding commonly decreases fluorescence intensity, the present study demonstrated that such strong interactions provide excellent conditions for fluorescence enhancement. Thus, this remarkable behaviour has potential application toward sensing of highly polar molecules, such as biogenic compounds.

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