Tunable Aggregation-induced Emission of Diphenyldibenzofulvenes

Materials and Instrumentations Fluorene, n-butyllithium (BuLi, 2.5 M in hexane), 2-aminobenzophenone, 4-dimethylaminopyridine (DMAP), acetic acid, trifluoroacetic acid, and N,N'-dicyclohexylcarbodiimide (DCC) were purchased from Aldrich and used as received. Solvents were purified by standard distillation procedures. 1 H and 13 C NMR spectra were measured on a Bruker ARX 300 or Varian 300 spectrometer using deuterated chloroform as solvent. Tetramethylsilane (TMS) was used as internal reference for the NMR analyses. Mass spectra were recorded on a triple quadrupole mass spectrometer (Finnigan TSQ7000). UV-vis absorption spectra were recorded on a Milton Roy Spectronic 3000 Array spectrophotometer and photoluminescence (PL) spectra were measured on a Perkin-Elmer LS 50B luminescence spectrometer with Xenon discharge lamp excitation. Transmission electron microphotograph (TEM) and electron diffraction (ED) patterns were taken on a JEOL 100CX TEM instrument.

X-ray diffraction intensity data were collected at 295 or 100 K on a Bruker-Nonius Smart Apex CCD diffractometer with graphite-monochromated Mo Kα radiation.Single crystal of 1 was grown from THF. Processing of the intensity data was carried out using the SAINT and SADABS routines, and the structure solution and refinement were carried out by the SHELXTL suite of X-ray programs (Version 6.10).

UV and PL Spectra
Stock solutions of 1-3 were 1.0 × 10 -3 M in acetonitrile.Sample mixtures for measuring the UV and PL spectra were prepared by adding 1 mL of a stock solution to 99 mL of acetonitrile or water under vigorous stirring at room temperature.The mixtures were stirred for half an hour prior to taking their spectra.Crystals of 1 and 2 were grown from THF/methanol mixtures, and their amorphous samples were prepared by rapidly freezing their isotropic melts by liquid nitrogen.

TEM Images and ED Patterns
One drop of an aggregate suspension in an acetonitrile/water mixture was placed on a copper grid coated with carbon.The deposit was dried in vacuum.The electron microscopy studies were performed using a JEOL 100CX TEM instrument.
Fig. S1Absorption and emission spectra of 1 in pure acetonitrile and acetonitrile/water mixtures.

Fig. S5
Fig. S5 TEM images (left) and ED patterns (right) of (A and B) crystalline and (C and D) amorphous

Fig. S11
Fig. S11 Perspective view of crystal packing of molecules of 1.