Supprting Infrmatin fr Design, Synthesis and Prperties f Cnfrmatinally Fixed Semiquinne Mnradical Species David A. Shultz, Jseph C. Slp and Gary Washingtn Table f Cntents 1. General Experimental Methds 2 2. NMR Spectra f Characterized Cmpunds....4 a. 2'(2-Hydrxyprpyl)-5-t-butyl-3,4-dimethxybiphenyl (3)..4 b. 3-t-Butyl-9,9-dimethylflurene rthquinne (6).5 c. 3-t-Butyl-1,2-dimethxy-9-flurenne (8) 6 d. 3-t-Butyl-1,2-dihydrxy-9-flurenne (9) 7 e. 5-t -Butyl-2'-nitr-2,3-dimethxymethylenxybiphenyl (12)...8 f. 4-t-Butyl-2,3-dimethxymethylenxycarbazle (13a)...9 g. 2-t-butyl-3,4-dimethxymethylenxycarbazle (13b)..10 h. 9N-methyl-4-t -butyl-2,3-dimethxymethylenxycarbazle (14) 11 i. 9N-methyl-4-t-butyl-2,3-dihydrxycarbazle (15) 12 j. 9N-methyl-4-t -butylcarbazle rthquinne (16)..13 k. 1-Hydrxydibenzfuran (19). 14 l. 1-Methxydibenzfuran (20)..15 m. 2-Hydrxy-1-methxydibenzfuran (21)......16 n. 1,2-Dimethxydibenzfuran (22)...17. 3-t-Butyl-1,2-dimethxydibenzfuran (23a).. 18 q. 8-t-Butyl-1,2-dimethxydibenzfuran (23b)......19 r. 3-t-Butyl-1,2-dihydrxydibenzfuran (24a)... 20 s. 8-t-Butyl-1,2-dihydrxydibenzfuran (24b) 21 t. DFT Cmputatinal Parameters fr cmpunds 7, 10, 17, 25a and 25b 22 u. Cyclic Vltammagrams fr 6F7 and 16F17.29 S1
1. General Experimental Methds. General Methds fr Preparatin f Methxy and Methxymethyl Prtected t - Butylbiphenyls. In a 125 ml Keldahl flask equipped with a N2 adapter and stir bar was added 1 equivalent f the phenyl halide, 1 equivalent f 3-t -butyl-4,sbis(methxymethylenxy)phenylbrnic ester (r 3-t-butyl-4,S-dimethxyphenylbrnic ester), 5 ml% Pd(PPh3)4, dry THF (20-S0mL), EtOH (1-10 ml), and 2M Na2C03 (1-1S ml). A reflux cndenser was added, the reactin mixture purged lox with N2 and refluxed fr 24h. Fllwing filtratin thrugh celite, the slvent was remved by evapratin under reduced pressure, extracted with Et20, washed with saturated brine slutin, cncentrated, and subjected t radial chrmatgraphy (silica gel w/s-40% ether/pet ether gradient) t aff<?rdthe prduct. General Prcedures fr the Preparatin f Catechls: Methd A. T a 100mL rund bttm flask equipped with a stir bar was added the t-butylbis(methxymethylenxy)biphenyl (- 1-3 mml), cncentrated HCI (2mL), and methanl (SO-70mL). A reflux cndenser was attached, and the mixture refluxed fr 18h with stirring under N2,prtected frm light. The slvent was remved by evapratin under reduced pressure. The residue was taken up in CH2Ch, extracted with saturated brine, and the bttm rganic layer dried ver Na2S04. The slvent was evaprated t dryness t affrd the catechl. S2
General Prcedures fr the Preparatin f Catechls: Methd B. T a 125 ml Keldahl flask equipped with a Nz adapter and stir bar was added the t-butyl-dimethxybiphenyl (1 equivalent, -0.5-1.5mml), distilled CHzClz(-lOmL), purged 3X with Nz, and cled t -7SC. Then, a 1.0M slutin f BBr3(3 equivalents, -1.5-4.5mml), was added drpwise slwly t the reactin mixture, which was then allwed t warm t rm temperature and stir fr 20h under Nz, prtected frm light. The reactin mixture was quenched with ice, washed with saturated brine and extracted with tw loml prtins f CHzClz. The rganic layers were cmbined, dried ver NaZS04, and the slvent evaprated t dryness t affrd the catechl. General Prcedures fr the Preparatin f Quinnes.30 T a 100 ml rund bttm flask equipped with a Nz adapter and stir bar was added the t -Butyl-dihydrxybiphenyl (0.3-0.7mml), F6tizn's Reagent (AgZC03 n celite) (3.0-5.0g, excess), NaZS04 (3.0-5.0g, excess), distilled CHzClz(20mL), and purged 3 times with Nz. The reactin mixture was stirred fr ISh under Nz. Filtratin thrugh celite and cncentratin under reduced pressure affrds the quinnes. General Prcedure fr the Preparatin f Semiquinnes. T a 20mL vial equipped with a stir bar in an inert atmsphere was added the catechl (1 equivalent, - 0.15mml), quinne (1 equivalent, - 0.15mml),dry THF (-5mL) and stirredfr 5 min. Then,KH (-2mg, 0.50mml) was added and the reactin mixture stirred fr 30 min. The resulting suspensin was filtered t remve excess KH, and a O.lmM slutin f the semiquinne in THF prepared fr EPR studies. S3
2. NMR Spectra f Characterized Cmpunds. ~{ ~{ -, \. 7.2449 6.8537 6.7884 _ L. 7.2630 r!2573 7.6071 --7.5809 ::r: w (J en -7.3443, 7.2630 - - \.. 7.2449' -'"'7.1377 -- 7.1126 ::r: U'I -6.8537-6.7880 3.9189 3.9132 ~3.8375 \.. 3.8324 w ru 1.5095 1.5049 4 '2 - S4 -
_181.151 _17S.!1' _158.017 _1"'.515 _151.13' _145.114 _131.145 _130.11',-12.7.151 '--121.483.--121.811 122.370 77.677 76.830 29.574 24.470 S5
$ (J ri- I 00-144.122-139._..r134.914 '""\.134.202-128.230...r 124.016-119.382-113.728 77.4583 77.2323 77.0333 76.6101..r61.8576 "'"\..61. 0026-35.9204 S6 ----
'\,,= C' / \- <,.. r \L / --...- - 194.846 CD _ a - 176.271 '-:>0 ::r::... 0 I b:i -= - 133.723 126.051-123.965-119.495-151.258 148.250-146.478-110.329 77.4431... 76.5932-34.2410-28.8671 - S7
.--- ~ CD J~ ~ 0"1 :{ ~ ~{ Ul ~ ) A :{ 1f w--l I '- \ " 3 N 11\_ / 0 z 3 IV 0... I OJ s:: ~{.I S8
{ 1?=- CD ] ( I... t:jj c {r t2 j -[., CD C> "3... 3. :{ I', r;-[ -...1_ r --J CD 01 --J ~ Ul w -- S9 ---
mi P, :{ :J '-- :""-{ w -...J -. I 70 'I :l\ 3 V-..3 I 3 0- -...J J:>. { y -...J i-u '"C 3: w ru -0 rj7 ~ ~.t) 1:... SlO
:{CDl?-= :{ { :-{ ---.J I ---.J CD ---.J 01.. --.,..' 01 ~{ t.n (] w I 7\J )I 3 0... 3,j;:.. --- --- - Sll - - - ---
144.063 140.462 129.969 128.705,-122.567 '--122.237 '---115.200,e-116.951 116.833 108.090 106.381 47.140 46.859 46.574 46.005 45.720 45.439 33.085 r-28.915 ~27. 947 S12
(» { \ : l :{ ",-7.713 7.70S r-7.&85 _7.U2 : {..., I I ;" cn-j I ~ ~ 7... I _7... - 7.4101 ;fj ~ \ _.,. S::'-.". w :{ :"" j ~ N '--7.U8 ~~~~~. :: \::7.222 U1 ~4.051 ~4. 048-0\ N <II <:> CD { <II -0-03 S13 1.308
;{ ~i..} ' J>. t ' ;.. f..~ ' ~ { {. ~ ~{. -... : { 'J... en 7.955 7.934 t;~9~;o f:i..932 r-.7.575 1:::::..7.540 7.203 7.038 7.035 '-7.929!--7.537 7.515 7.511 7.499 7.494 7.474 7.471 7.448 7.442 7.384 7.382 7.360 7.356 7.335-7.259 7.255 7.228 5.313 en = ;., :r: :., w ] - c c: --== c c:::: N :1 ( c C J,- {.,- C -.- -- I r S14
en Ul... <=> N en Ul Ul Ul A Ul S15
::t (") ::t... J CD (j") (Jl (j") (Jl (Jl (Jl - 516
C» 0 { ::r: '" () { r { 0 '-I \ J_ 7.576 r,.m 7.535 7.567 7.562 7.549 \2.545 7.543 1.531 () ::r: '" C') (J1 ~ ~7.28S......~ "\ 7.395.7.393 \-'.'72 \.-?368 7.338 7.335 7.314 \.-'.310 C') _6,'" 6.!l50 (J1 (J1 U1 (J1 4.208 N U1 "" { "C "C 3 - - 517 3.973
~{" r \ : { F \ '.z ~{~JF \ en (') ::r:... CJ'1 4.188 3.973 N "C "C 3 --- - --- S18 - ---
:x:: '" (") '- ---... n it-,.105 519
Ī ::r: 0 { 1 r=- { N =.j;>. M- { \ j,,-.., (" _7.848 :1 7.401 - _7.373 _7.440 :-1 r- N _1.25' ml I ; { 1 \ j j (" I _,.,so 6.'22 U1 _5.4'6 w N S20
:r: + en.697,71.272 '--76.846 31.866 S21
Gaussian 98W ********************************************* Gaussian 98: x86-win32-g98reva.9 19-Apr-2000 31-Aug-2006 ********************************************* Fr Optimizatin f all Mlecules #P ub3lyp/epr-ii pt density=current Fr Frequency calculatins f all Mlecules #P ub3lyp/epr-ii freq gem=checkpint S22
SQ 7 - crdinates f ptimized structure Input rientatin: Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z 1 6 0 3.502535-2.742657-0.000610 2 6 0 4.470343-1.722270-0.000360 3 6 0 4.069865-0.368235-0.000044 4 6 0 2.712168-0.051835 0.000017 5 6 0 1.732704-1.082838-0.000236 6 6 0 2.131020-2.432191-0.000550 7 6 0 2.036202 1.320878 0.000333 8 6 0-0.880108-1.077892-0.000256 9 6 0 2.401319 2.137193-1.266008 10 6 0 2.401290 2.136592 1.267070 11 6 0 0.405580-0.461052-0.000101 12 6 0 0.560676 0.925141 0.000224 13 8 0-2.965562 1.895685 0.000345 14 6 0-2.040069-0.315901-0.000093 15 6 0-1.945084 1.161498 0.000256 16 6 0-0.568373 1.815596 0.000422 17 8 0-0.451370 3.072568 0.000748 18 6 0-3.438616-0.965630-0.000261 19 6 0-3.370900-2.510072-0.000779 20 6 0-4.224365-0.529537-1.266932 21 6 0-4.224247-0.530360 1.266765 22 1 0 3.819391-3.783985-0.000853 23 1 0 5.527930-1.977106-0.000409 24 1 0 4.822134 0.419045 0.000149 25 1 0 1.390163-3.228651-0.000744 26 1 0-0.930604-2.162543-0.000516 27 1 0 1.805429 3.053231-1.284642 28 1 0 2.184127 1.561343-2.171331 29 1 0 3.467004 2.399233-1.270188 30 1 0 1.805395 3.052619 1.286127 31 1 0 3.466973 2.398635 1.271394 32 1 0 2.184082 1.560310 2.172113 33 1 0-4.388679-2.918712-0.000861 34 1 0-2.856961-2.895494 0.886761 35 1 0-2.857052-2.894896-0.888631 36 1 0-4.314554 0.556815-1.297771 37 1 0-5.228603-0.974852-1.263911 38 1 0-3.704816-0.864240-2.172607 39 1 0-4.314438 0.555974 1.298308 40 1 0-3.704611-0.865639 2.172176 41 1 0-5.228485-0.975671 1.263554 S23
SQ 10 - crdinates f ptimized structure Input rientatin: Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z 1 6 0 3.810271-2.356336-0.003772 2 6 0 4.718614-1.280228-0.001755 3 6 0 4.243407 0.048398 0.000514 4 6 0 2.868073 0.264442 0.000697 5 6 0 1.947129-0.812801-0.001303 6 6 0 2.418760-2.133990-0.003564 7 6 0 2.095697 1.568994 0.002774 8 8 0 2.618469 2.686047 0.004966 9 6 0 0.673541 1.164878 0.002090 10 6 0 0.589059-0.245444-0.000429 11 6 0-0.527369 1.978433 0.003491 12 6 0-1.872763 1.195427 0.002249 13 6 0-1.863540-0.281126-0.000571 14 6 0-0.639658-0.946182-0.001769 15 8 0-0.559971 3.216265 0.005185 16 6 0-3.204911-1.039246-0.002099 17 8 0-2.931295 1.853896 0.003279 18 6 0-4.022646-0.664782-1.268429 19 6 0-3.009183-2.572432-0.005702 20 6 0-4.022240-0.670696 1.266234 21 1 0 4.189483-3.376401-0.005512 22 1 0 5.788166-1.478621-0.001968 23 1 0 4.925403 0.895430 0.002073 24 1 0 1.731749-2.977361-0.005115 25 1 0-0.606991-2.031246-0.003786 26 1 0-4.984099-1.195103-1.267929 27 1 0-3.476416-0.949485-2.175129 28 1 0-4.209170 0.409137-1.297654 29 1 0-3.989153-3.063797-0.006756 30 1 0-2.465867-2.916324 0.881210 31 1 0-2.466036-2.912173-0.894316 32 1 0-4.983594-1.201192 1.263683 33 1 0-4.208929 0.403044 1.300413 34 1 0-3.475610-0.959421 2.171421 S24
SQ 17 - crdinates f ptimized structure Input rientatin: Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z 1 6 0-3.841031-2.393992-0.005485 2 6 0-4.693386-1.265743 0.006976 3 6 0-4.167380 0.036950 0.015772 4 6 0-2.770286 0.186323 0.011831 5 6 0-1.887949-0.948383-0.000820 6 6 0-2.446040-2.242441-0.009415 7 7 0-2.011013 1.338754 0.018481 8 6 0 0.495184 1.864967 0.013647 9 6 0-0.652550 0.984631 0.010600 10 6 0-0.544030-0.419889-0.001426 11 6 0 1.841954 1.174002 0.002913 12 6 0 1.906288-0.306862-0.009554 13 6 0 0.737774-1.049813-0.011372 14 8 0 2.880631 1.887888 0.004835 15 8 0 0.401548 3.127345 0.024433 16 6 0 3.293985-0.980636-0.020271 17 6 0-2.556223 2.685058 0.031242 18 6 0 4.092471-0.570112 1.246938 19 6 0 3.198569-2.523419-0.032580 20 6 0 4.082993-0.549281-1.286496 21 1 0-4.274973-3.391643-0.012111 22 1 0-5.772265-1.406043 0.009805 23 1 0-4.825584 0.901883 0.025317 24 1 0-1.800684-3.118236-0.019033 25 1 0 0.769805-2.134972-0.020455 26 1 0 5.089930-1.030658 1.235354 27 1 0 3.571157-0.905795 2.151333 28 1 0 4.198893 0.514543 1.287522 29 1 0-1.714769 3.378331 0.033907 30 1 0-3.173008 2.845015 0.925636 31 1 0-3.179195 2.859429-0.856151 32 1 0 4.208599-2.950966-0.039793 33 1 0 2.674327-2.891793-0.921415 34 1 0 2.680838-2.906344 0.853918 35 1 0 5.080458-1.009947-1.289998 36 1 0 4.189226 0.535899-1.309980 37 1 0 3.554861-0.869997-2.192364 S25
SQ 25a - Crdinates f ptimized structure Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z 1 6 0 4.199000-1.863922-0.000059 2 6 0 2.794923-1.880719-0.000017 3 6 0 2.097494-0.655782-0.000032 4 6 0 2.846610 0.554728-0.000092 5 6 0 4.240973 0.588725-0.000135 6 6 0 4.915818-0.647102-0.000117 7 6 0 0.724734 1.151627-0.000051 8 8 0 2.027779 1.646636-0.000107 9 6 0 0.709683-0.244475-0.000002 10 6 0-0.444340 1.991111-0.000046 11 6 0-1.755525 1.217264 0.000111 12 6 0-0.531489-0.951413 0.000045 13 6 0-1.736938-0.267477 0.000068 14 8 0-0.405485 3.246320-0.000081 15 8 0-2.831581 1.868621-0.000004 16 6 0-2.904681-2.552227 0.000182 17 6 0-3.900925-0.640743-1.267021 18 6 0-3.900922-0.640608 1.267188 19 6 0-3.085702-1.017123 0.000103 20 1 0 4.746541-2.803950-0.000046 21 1 0 2.255811-2.825149 0.000027 22 1 0 4.774373 1.534875-0.000181 23 1 0 6.003101-0.662399-0.000149 24 1 0-0.503909-2.036002 0.000053 25 1 0-3.889481-3.034674 0.000161 26 1 0-2.364293-2.898770 0.888108 27 1 0-2.364213-2.898852-0.887663 28 1 0-4.870189-1.157736-1.263370 29 1 0-3.358156-0.938123-2.172128 30 1 0-4.069610 0.436168-1.299131 31 1 0-4.870197-1.157581 1.263580 32 1 0-4.069585 0.436310 1.299197 33 1 0-3.358163-0.937913 2.172325 S26
SQ 25b - crdinates f ptimized structure Input rientatin: Center Atmic Atmic Crdinates (Angstrms) Number Number Type X Y Z 1 6 0-2.034140 2.780043 0.000235 2 6 0-2.771519 1.576014 0.000278 3 6 0-2.151742 0.307533 0.000260 4 6 0-0.745687 0.341145 0.000130 5 6 0 0.027368 1.534387 0.000053 6 6 0-0.634397 2.777945 0.000131 7 6 0-2.931055-1.019811 0.000257 8 8 0 0.067592-0.761693-0.000063 9 6 0 2.520615-1.175995-0.000334 10 6 0 1.379492-0.292413-0.000160 11 6 0 1.409753 1.106494-0.000063 12 6 0 3.850370-0.434103-0.000288 13 6 0 3.826717 1.032588-0.000261 14 6 0 2.668340 1.785788-0.000140 15 8 0 2.429968-2.428717-0.000363 16 8 0 4.934776-1.066869-0.000523 17 6 0-2.564622-1.839049-1.265992 18 6 0-4.458447-0.790784 0.000097 19 6 0-2.564887-1.838959 1.266644 20 1 0-2.572982 3.725308 0.000275 21 1 0-3.854333 1.640411 0.000340 22 1 0-0.073085 3.708973 0.000092 23 1 0 4.804013 1.511738-0.000335 24 1 0 2.706227 2.873437-0.000104 25 1 0-1.497781-2.067243-1.294699 26 1 0-2.822461-1.281150-2.173147 27 1 0-3.119514-2.785372-1.276173 28 1 0-4.970485-1.759398 0.000103 29 1 0-4.787153-0.240039-0.887759 30 1 0-4.787321-0.239936 0.887827 31 1 0-1.498064-2.067187 1.295589 32 1 0-3.119815-2.785262 1.276792 33 1 0-2.822894-1.280980 2.173703 S27
SQ Ttal Energy (Hartrees) Number f Imaginary Vibratinal Frequencies 7 E(UB+HF-LYP) = -886.723263738 H - NImag=0 V/T = 2.0080 S**2 = 0.7607 10 E(UB+HF-LYP) = -882.120454270 H NImag=0 -V/T = 2.0078 S**2 = 0.7634 17 E(UB+HF-LYP) = -863.452196742 H NImag=0 -V/T = 2.0079 S**2 = 0.7607 25a E(UB+HF-LYP) = -843.997993722 H NImag=0 -V/T = 2.0077 S**2 = 0.7613 25b E(UB+HF-LYP) = -843.999259350 H NImag=0 -V/T = 2.0077 S**2 = 0.7621 All ptimized structures have zer imaginary frequencies. S28
9,9-Dimethyl Flurene Quinne-Semiquinne (6F7) and N-Methyl Carbazle Quinne-Semiquinne (16F17) Cyclic Vltammagrams. a 6F7 16F17-0.2-0.4-0.6-0.8-1 -1.2 Reductin Ptential (V) a. Ferrcene-ferrcenium cuple mitted fr clarity. Experimental parameters: Samples (6F7), (16F17): IP: -0.30V V1: -1.3V V2: +0.30V FP: -0.3V Standard (ferrcenefferrcenium): IP: -0.50V V1: -1.3V V2: +0.20V FP: -0.5V S29