SUPPORTIG IFORMATIO Effective PET and ICT Switching of Boradiazaindacene Emission: A Unimolecular, Emission Mode Molecular Half-Subtractor with Reconfigurable Logic Gates Ali Coşkun, Erhan Deniz and Engin U. Akkaya* 0.14 0.12 0.10 Acid Free Base Absorbance 0.08 0.06 0.04 0.02 0.00 500 550 600 650 700 Wavelength (nm) Figure S1. Absorption spectra of Compound 2 upon addition of Acid (HClO 4 ) and Base (t-buo - ) S1
Table S1. Quantum yields in THF solution Compounds Quantum yield Compound 2 0.25 Compound 2 + HClO 4 0.84 Compound 2 + t-buo - 0.032 All dyes were excited at 500 nm, and all spectra were corrected, excitation and emission slits were both set at 5 nm. Rhodamine 6G was used as the reference compound in quantum yield measurements, Quantum yield of rhodamine is 0.95 in ethanol. (see: Du, H.; Fuh, R. A.; Li, J.; Corkan, A.; Lindsey, J. S. Photochem. Photobiol. 1998, 68, 141-142.) Corrections for refractive indices were done. x y z 0 0 1 0 1 0 1 0 0 1 1 1 Truth table for positive logic XOR gate x z y Positive logic XOR gate x y z 0 0 0 0 1 1 1 0 1 1 1 0 Truth table for XOR gate with negative logic applied on the output. Figure S2. Truth tables and logic diagrams. XOR logic gate with negative logic applied on the output. S2
Half-Subtractor contains XOR and IHIBIT (OT and AD) logic gates. The circuit has two outputs labelled DIFF and BORROW. A truth table for the circuit looks like following: A B BORROW DIFF 0 0 0 0 0 1 1 1 1 0 0 1 1 1 0 0 Cleary this circuit is performing binary subtraction of B from A (A-B, recalling that in binary 0-1 = 1 borrow 1). Such a circuit is called a half-subtractor, the reason for this is that it enables a borrow out of the current arithmetic operation but no borrow in from a previous arithmetic operation. Figure S3. Subtraction using logic gates S3
EXPERIMETAL PROCEDURES General All chemicals and solvents purchased from Aldrich were used without further purification. 1H MR and 13C MR spectra were recorded using a Bruker DPX-400 in CDCl3 or DMSO-d 6 with TMS as internal reference. Absorption spectrometry was performed using a Varian spectrophotometer. Steady state fluorescence and time-resolved fluorescence measurements were conducted using a Varian Eclipse spectrofluorometer and a PTI TimeMaster system, respectively. Column chromatography of all products was performed using Merck Silica Gel 60 (particle size: 0.040 0.063 mm, 230 400 mesh ASTM). Reactions were monitored by thin layer chromatography using fluorescent coated aluminum sheets. Solvents used for spectroscopy experiments were spectrophotometric grade. HRMS (FAB) measurements were done at the Kent Mass Spectrometry Laboratory, Kent, U.K. Synthesis: 4,4-difluoro-8-(4 -hydroxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (1b): 2,4-dimethylpyrrole (500 mg, 5.26 mmol) and 4-hydroxybenzaldehyde (318 mg, 2.6 mmol) were dissolved in 300 ml absolute CH 2 Cl 2 under 2 atmosphere. One drop of TFA was added and the solution stirred at r.t. until TLC-control showed the complete consumption of the aldehyde. At this point, a solution of tetrachlorobenzoquinone (640 mg, 2.6 mmol)in 100 ml absolute CH 2 Cl 2 was added, stirring was continued for 15 min followed by the addition of 3 ml of Et 3 and 3 ml of BF 3.OEt 2 respectively. After stirring for 30 min the reaction mixture was washed with water, dried over a 2 SO 4 and evaporated to dryness. The residue was chromatographed on silica gel( eluent 1 Ethyl Acetate: 1 Hexane ) to afford 548 mg 1b as orange needles. Yield 62%. 1 H MR (400 MHz, CDCl 3 ) δ 7.05 (d, J= 8.6 Hz, 2H), 6.87 (d, J= 8.6 Hz, 2H), 5.90 (s, 2H), 2.48 (s, 6H), 1.37 (s, 6H); S4
13 C MR (100 MHz, CDCl 3 ) δ 156.3, 155.3, 143.3, 143.1, 141.7, 131.8, 129.4, 121.1, 118.9, 116.1, 14.5. H H O 1. TFA, absolute CH 2 Cl 2, 2, R.T. 2. Tetrachlorobenzoquinone 3. Et 3, BF 3.OEt 2 B F F 1b 3-{2 -(4 -dimethylaminophenyl)ethenyl}-4,4-difluoro-8-(4 -hydroxyphenyl)-1,3,5,7- tetramethyl-4-bora-3a,4a-diaza-s-indacene (2): Compound 1b (224 mg, 0.66 mmol) and dimethylaminobenzaldehyde (98 mg, 0.66 mmol) were refluxed in a mixture of toluene (45 ml), glacial acetic acid (0.5 ml), piperidine (0.6 ml) and small amount of Mg(ClO 4 ) 2. Any water formed during the reaction, was removed azeotropically by heating overnight in a Dean-Stark apparatus. Crude product concentrated under vacuum, then purified by silica gel column chromatography (first EtOAc: Hexane (1:1), then CH 2 Cl 2 : Me (99:1)). The blue colored fraction was collected and the solvent was removed under reduced pressure to yield the desired material 2.( 118 mg, 38 %). 1 H MR (400 MHz, DMSO-d 6 ) δ 9.79 (s,1h), 7.49-7.44 (m, 3H), 7.26 (d, J=16.2 Hz, 1H), 7.15 (d, J=7.9 Hz, 2H), 6.94 (d, J=7.9 Hz, 2H), 6.90 (s, 1H), 6.79 (d, J=8.3 Hz, 2H), 6.12 (s, 1H), 3.00 (s, 6H), 2.47 (s, 3H), 1.49 (s, 3H), 1.44 (s, 3H); 13 C MR (100 MHz, DMSO-d 6 ) δ 158.0, 154.1, 151.2, 139.6, 138.4, 129.3, 128.8, 124.6, 123.6, 122.9, 120.3, 119.2, 117.9, 115.9, 113.9, 112.8, 112.2, 111.1, 110.9, 54.9, 14.4, 14.2, 13.9; FAB-HRMS calcd for 471.22934, found 471.229691 = 0.75 ppm S5
B F F H O Ac/Piperidine in Toluene reflux, 24 h Dean-Stark trap B 1b 2 F F S6
B F F * * H 2 O S7
B F F * * Benzene S8
B F F S9
B F F S10