[structure: see text] Novel ter(9,9-ditolylfluorene) analogues containing thiophene and pyridine rings embedded as functional constituents within the parent hydrocarbon backbone have been synthesized. These new molecules exhibit highly efficient photoluminescence and high thermal and morphological stability. The electronic structure of the terfluorene backbone is significantly perturbed, which allows modulation of the backbone energy levels.
A new right angle-shaped ligand, 2,2′-bis(4-pyridyl)-9,9′-spirobifluorene (L), is designed and synthesized. Treatment of L with silver(I) ions leads to linear polymeric metal-organic frameworks, [Ag(L) 2 ] + (1), that feature square subunits. Single-crystal X-ray analysis reveals that [Ag(L) 2 ] + has a one-dimensional double-stranded polymeric chain comprising square grids with cavity dimensions of ca. 8 Å × 8 Å. By π-π stacking of adjacent double-stranded chains, the structure is extended into a two-dimensional (2D) layer framework with a unique quasiaperture (dimensions of ca. 14 Å × 8 Å). Each 2D layer is inclined and mutually interpenetrated, which gives rise to the three-dimensional interlocked network structure. Compound 1‚(BF 4 )(CH 3 OH) crystallizes in the monoclinic system, space group C2/c, with chemical formula C 71 H 49 N 4 OBF 4 Ag, a ) 25.709(1) Å, b ) 14.4164(6) Å, c ) 15.6865-(7) Å, β ) 109.220(2)°, and Z ) 4.
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