Supplementary Information - Royal Society of Chemistry · 1! Supplementary Information...

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Supplementary Information

Ferromagnetic Spin-Delocalized Electron Donors for

Multifunctional Materials: π-Conjugated Benzotriazinyl

Radicals

Bin Yan,a Jordan Cramen,a Robert McDonald,b and Natia L. Franka*

* aDepartment of Chemistry, Box 3065, University of Victoria, Victoria, British Columbia,

V8W 3V6, Canada.b b Department of Chemistry, University of Alberta, 11227

Saskatchewan Drive NW, Edmonton, Alberta, Canada, T6G 2G2

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2011

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Experimental.

General. All starting materials were purchased from commercial suppliers (Aldrich,

Acros, and Lancaster) and used without purification. The solvents were freshly distilled

or dried according to standard procedures before use. All reactions were monitored by

TLC performed on plastic-backed silica gel plates, and compounds were visualized under

UV light. For chromatography silica gel 60 was used. 1H and 13C NMR spectra were

recorded with a Bruker AMX spectrometer (300 MHz) . Chemical shifts are given in

parts per million (δ) downfield from Me4Si as the internal standard. FT-IR spectra were

measured as KBr pellets on a Perkin Elmer Spectrum One Spectrometer. Mass spectra

were recorded on a Finnigan 3300 or Kratos Concept II spectrometer using electron

impact EI sources. Electronic absorption spectroscopy was carried out on an Agilent 8453

UV-Vis spectrometer with photodiode array and Peltier temperature controller. Elemental

analyses were performed by Canadian Microanalytical Services, Desert Analytics, or

University of British Columbia.

Syntheses.

3-Vinylbenzaldehyde (2). A mixture of 3-bromobenzaldehyde (1.2 g, 6.5 mmol),

tributylethenylstannane (2.1 g, 6.5 mmol), and Pd(PPh3)4 (150 mg, 0.13 mmol) in 25 mL

dried DMF was stirred at 100 ºC for 12 hours. After cooling to room temp, the mixture

was filtered and the filtrate was poured into water, and extracted with ethyl ether (3×50

mL). The combined organic layers were dried over MgSO4. After removal of the solvent,

the crude product was purified by column chromatography on silica gel (5% EtOAc in

hexanes) to give a colorless oil as the product (0.65 g, 4.9 mmol, 76%). 1H NMR (300

MHz, CDCl3): δ 10.00 (s, 1H), 7.90 (s, 1H), 7.76 (d, J = 9 Hz, 1H), 7.66 (d, J = 6 Hz, 1H),

7.49 (t, J = 7.5 Hz, 1H), 6.76 (dd, J = 18, 12 Hz, 1H), 5.86 (d, J = 18 Hz, 1H), 5.35 (d, J =

12 Hz, 1H). 13C NMR (300 MHz, CDCl3): δ 192.3, 138.5, 136.7, 135.6, 132.0, 129.2,

129.1, 127.1, 115.7. 1-Phenyl-2-(3-vinylbenzylidene)hydrazine (3a). To a solution of 2 (2.65 g, 0.02

mmol) in benzene (50 mL) was added phenylhydrazine (2.16 g, 0.02 mmol) and the reaction mixture was stirred at room temperature for 6 h. The solvent was removed on rotavap, and the residue was purified by column chromatography on silica gel with 10-


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20% EtOAc in hexanes as eluent to give a pale yellow solid as the product (2.4 g, 10.8 mmol, 54%). m.p. 127-128 °C. 1H NMR (300 MHz, CDCl3): δ 7.67 (s, 2H), 7.62 (s, 1H), 7.54 (d, J = 6.6 Hz, 1H), 7.34-7.24 (m, 4H), 7.11 (d, J = 7.8 Hz, 2H), 6.87 (t, J = 7.5 Hz, 1H), 6.74 (dd, J = 17.7, 11.1 Hz, 1H), 5.79 (d, J = 17.7 Hz, 1H), 5.28 (d, J = 11.1 Hz, 1H). 13C NMR (300 MHz, CDCl3): δ 144.8, 138.1, 137.3, 136.8, 135.7, 129.5, 129.0, 126.4, 125.9, 124.2, 120.4, 114.6, 113.0. IR (KBr pellet, cm-1): 3318 (m), 3051 (w), 1838 (w), 1627 (w), 1596 (s), 1569 (s), 1513 (s), 1484 (s), 1447 (m), 1395 (m), 1349 (m), 1298 (m), 1260 (s), 1244 (s), 1173 (m), 1139 (s), 1073 (m), 998 (m), 917 (s), 884 (m), 804 (s), 752 (s), 717 (m), 693 (s), 674 (m). MS (EI) m/z: 222 (M+), 223 ((M+1)+). Anal. Calcd for C15H14N2: C, 81.05; H, 6.35; N, 12.60. Found: C, 80.43; H, 6.42; N, 12.57.

N'-Phenyl-3-vinylbenzohydrazonoyl chloride (4a). To a solution of NCS (4 g, 0.03

mol) in CH2Cl2 (100 mL) at 0◦C was added (CH3)2S (3.72 g, 0.06 mol) and the reaction

solution was cooled to -78◦C. To this solution was added a solution of 3a (4.44 g, 0.02

mol) in CH2Cl2 (50 mL) and the reaction mixture was stirred for 1 h, allowed to warm to

room temperature and stirred for 2 h, then quenched with cold water, extracted with

CH2Cl2, washed with brine, and dried over MgSO4. The solvent was removed on rotavap,

and the residue was crystallized from ether/hexanes to give a red solid as the product

(2.93g, 11.4 mmol, 57%). m.p. 71-73 °C. 1H NMR (300 MHz, CDCl3): δ 8.04 (s, 1H),

7.92 (s, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.43-7.28 (m, 4H), 7.17 (d, J = 7.5 Hz, 2H), 6.93 (t,

J = 6.8 Hz, 1H), 6.76 (dd, J = 17.4, 10.8 Hz, 1H), 5.82 (d, J = 17.4 Hz, 1H), 5.31 (d, J =

10.8 Hz, 1H). 13C NMR (300 MHz, CDCl3): δ 143.5, 138.0, 136.6, 134.9, 129.6, 128.8,

127.0, 126.0, 124.7, 124.6, 121.4, 115.0, 113.6. IR (KBr pellet, cm-1): 3310 (m), 3049 (w),

2923 (w), 1630 (w), 1600 (s), 1579 (s), 1504 (s), 1435 (s), 1384 (m), 1313 (m), 1291 (w),

1246 (s), 1176 (m), 1138 (s), 1102 (m), 1071 (m), 988 (s), 912 (m), 900 (s), 887 (m), 792

(m), 776 (m), 750 (s), 713 (w), 692 (s). MS (EI) m/z: 256 (M+), 257 ((M+1)+), 258

((M+2)+). Anal. Calcd for C15H13ClN2: C, 70.18; H, 5.10; N, 10.91. Found: C, 69.95; H,

5.32; N, 10.78.

N,N'-Diphenyl-3-vinylbenzohydrazonamide (5a). A solution of 4a (0.26 g, 1.01

mmol), aniline (0.1 g, 1.08 mmol) and TEA (1 mL) in 25 mL ethanol was refluxed

overnight, the solvent was removed on rotavap and added 50 mL cold water, extracted

with CH2Cl2, washed with brine, dried over MgSO4, purified by column on silica gel (4%

EtOAc in hexanes) to give a pale yellow solid as the product (0.137 g, 0.44 mmol, 43%).


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m.p. 109-110 °C. 1H NMR (300MHz, CDCl3): δ 7.76 (s, 1H), 7.59-7.57 (m, 2H), 7.39 (d,

J = 8.1 Hz, 1H), 7.32-7.20 (m, 5H), 7.11 (d, J = 8.4, 2H), 6.93-6.84 (m, 2H), 6.77-6.67 (m,

3H), 5.74 (d, J = 17.7 Hz, 1H), 5.58 (s, 1H), 5.26 (d, J = 11.1 Hz, 1H). 13C NMR

(300MHz, CDCl3): δ 145.1, 141.6, 138.1, 137.1, 136.7, 135.4, 129.7, 129.4, 128.9, 126.6,

126.1, 124.6, 121.1, 120.4, 116.2, 114.7, 113.5. IR (KBr pellet, cm-1): 3329 (s), 3304 (s),

3044 (w), 1597 (s), 1564 (m), 1495 (s), 1426 (m), 1400 (m), 1384 (m), 1331 (w), 1295

(m), 1243 (s), 1197 (s), 1157 (s), 1061 (m), 993 (m), 980 (w), 917 (m), 904 (m), 884 (w),

804 (m), 753 (s), 718 (w), 696 (s). MS (EI) m/z: 313 (M+), 314 ((M+1)+). Anal. Calcd for

C21H19N3: C, 80.48; H, 6.11; N, 13.41. Found: C, 80.16; H, 6.07; N 13.25.

1-Phenyl-3-(3-vinylphenyl)-1,2,4-benzotriazin-4-yl (1a). To the solution of 5a (0.1 g,

0.32 mmol) in 25 mL ethanol was added HgO (0.5 g, 2.3 mmol). The reaction mixture

was refluxed for 1 hour and further stirred for 1 h at room temperature, followed by

filtration to remove the solid. The dark solution was stirred in air for 4 days. Removal of

the ethanol and purification by column chromatography on silica gel (5% EtOAc in

hexanes) yields a black solid as the product (0.063 g, 0.203 mmol, 63%). m.p. 85-86 °C.

IR (KBr pellet, cm-1): 3051 (w), 1626 (w), 1593 (w), 1480 (m), 1439 (w), 1385 (s), 1355

(m), 1362 (w), 1310 (w), 1250 (w), 1209 (w), 1194 (m), 1170 (w), 1081 (w), 1025 (w),

991 (m), 897 (m), 842 (w), 820 (w), 806 (m), 755 (m), 723 (w), 696 (s). UV-vis (CH2Cl2)

λmax nm (ε×10-4): 260 (2.31), 318 (0.51), 370 (0.39), 428 (0.21), 491 (0.09), 550 (sh). MS

(EI) m/z: 310 (M+), 311 ((M+1)+). Anal. Calcd for C21H16N3: C, 81.27; H, 5.20; N, 13.54.

Found: C, 81.43; H, 5.39; N, 13.56.

1-(4-Bromophenyl)-2-(3-vinylbenzylidene)hydrazine (3b). To a solution of 2 (1.32 g,

10 mmol) in benzene (50 mL) was added 4-bromophenylhydrazine hydrochloride (2.23 g,

10 mmol) and 1.5 mL TEA, the reaction mixture was stirred at room temperature for 12 h.

After removal of the solvent en vacuo, the residue was purified by flash chromatography

on silica gel with CH2Cl2 as eluent and recrystallized from hexanes to give a pale yellow

crystal as the product (2.2 g, 7.31 mmol, 73%). m.p. 87-88 °C. 1H NMR (300 MHz,

CDCl3): δ 7.66-7.65 (m, 2H), 7.60 (s, 1H), 7.54-7.51 (m, 1H), 7.38-7.29 (m, 4H), 6.99

(dd, J = 6.6, 2.1 Hz, 2H), 6.74 (dd, J = 17.4, 10.5 Hz, 1H), 5.79 (d, J = 17.4 Hz, 1H), 5.29

(d, J = 10.5 Hz, 1H). 13C NMR (300 MHz, CDCl3): δ 143.8, 138.2, 138.1, 136.7, 135.4,

132.3, 129.1, 126.7, 126.0, 124.3, 114.7, 114.6, 112.2. IR (KBr pellet, cm-1): 3319 (w),


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3082 (w), 2961 (w), 1591 (s), 1509 (s), 1481 (s), 1394 (w), 1289 (m), 1258 (s), 1245 (s),

1168 (m), 1137 (s), 1096 (m), 1069 (m), 995 (m), 912 (m), 822 (s). MS (EI) m/z: 300

(M+), 302 ((M+2)+). Anal. Calcd for C15H13BrN2: C, 59.82; H, 4.35; N, 9.30. Found: C,

59.86; H, 4.64; N, 9.05.

N'-(4-Bromophenyl)-3-vinylbenzohydrazonoyl chloride (4b). To a solution of NCS

(2 g, 0.015 mol) in CH2Cl2 (100 mL) at 0 °C was added (CH3)2S (2 g, 0.032 mol) and the

reaction mixture was stirred for 15 min and then cooled to -78 °C. To this solution was

added a solution of 3b (3 g, 0.01 mol) in CH2Cl2 (50 mL) and the mixture was stirred for

1 h at this temperature, then warmed to room temperature, stirred for 2 h, and quenched

with cold water. The combined organic extracts were washed with brine, dried over

MgSO4, and purified by flash chromatography on silica gel with CH2Cl2 as eluent to give

a pale brown powder as the product (2.26 g, 6.74 mmol, 67%). m.p. 78-80 °C. 1H NMR

(300 MHz, CDCl3): δ 8.02 (s, 1H), 7.89 (s, 1H), 7.81-7.78 (m, 1H), 7.44-7.33 (m, 4H),

7.05 (d, J = 4.5 Hz, 2H), 6.76 (dd, J = 17.7, 10.8 Hz, 1H), 5.82 (d, J = 17.7 Hz, 1H), 5.32

(d, J = 10.8 Hz, 1H). 13C NMR(300 MHz, CDCl3): δ 142.6, 138.1, 136.5, 134.7, 132.4,

128.9, 127.3, 126.1, 125.7, 124.7, 115.3, 115.1, 113.4. IR (KBr pellet, cm-1): 3321 (m),

2924 (w), 1594 (s), 1486 (s), 1395 (m), 1314 (m), 1245 (s), 1169 (m), 1141 (s), 1096 (m),

1069 (s), 995 (m), 979 (s), 899 (s), 813 (s). MS (EI) m/z: 334 (M+), 336 ((M+2)+), 338

((M+4)+). Anal. Calcd for C15H12BrClN2: C, 53.68; H, 3.60; N, 8.35. Found: C, 53.85; H,

3.86; N, 8.05.

N'-(4-Bromophenyl)-N-phenyl-3-vinylbenzohydrazonamide (5b). A solution of 4b

(2.25 g, 6.7 mmol), aniline (1 g, 10.75 mmol) and 1 mL TEA in CH3CN was stirred for

12 h at room temperature, then purified by column chromatography on silica gel with 4%

EtOAc in hexanes as eluent to give a pale yellow solid as the product (0.87 g, 2.22 mmol,

33%). m.p. 92-93 °C. 1H NMR (300 MHz, CDCl3): δ 7.73 (s, 1H), 7.56 (d, J = 7.5 Hz,

1H), 7.48 (s, 1H), 7.40 (d, J = 7.5 Hz, 1H), 7.35-7.20 (m, 5H), 7.00-6.89 (m, 3H), 6.76-

6.67 (m, 3H), 5.74 (d, J = 17.7 Hz, 1H), 5.60 (s, 1H), 5.26 (d, J = 11.1 Hz, 1H). 13C NMR

(300 MHz, CDCl3): δ 144.2, 141.3, 138.1, 137.8, 136.7, 135.2, 132.2, 129.7, 128.9, 126.9,

126.1, 124.7, 121.4, 116.4, 115.1, 114.8, 112.1. IR (KBr pellet, cm-1): 3340 (m), 3254 (w),

3051 (w), 1588 (s), 1569 (s), 1486 (s), 1437 (m), 1417 (m), 1384 (s), 1361 (s), 1302 (s),

1289 (m), 1245 (s), 1201 (m), 1169 (m), 1133 (m), 1062 (m), 995 (m), 918 (m), 906 (m),


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820 (s), 804 (s), 759 (m), 748 (m), 708 (s). MS (EI) m/z: 391 (M+), 393 ((M+2)+). Anal.

Calcd for C21H18BrN3: C, 64.30; H, 4.62; N, 10.71. Found: C, 64.11; H, 4.55; N, 10.69.

1-(4-Bromophenyl)-3-(3-vinylphenyl)-1,2,4-benzotriazin-4-yl (1b). DBU (0.5 mL)

was added to a solution of 5b (0.87 g, 2.22 mmol) in ethanol (50 mL), and the mixture

was stirred at room temperature for 2 days. After removal of the solvent, the residue was

subject to column chromatography on silica gel with 5% EtOAc in hexane as eluent to

give a shiny black solid as the product (0.61 g, 1.57 mmol, 71%). m.p. 114-115 °C. IR

(KBr pellet, cm-1): 3057 (w), 1578 (w), 1479 (s), 1439 (w), 1384 (s), 1308 (w), 1251 (w),

1194 (m), 1089 (w), 1068 (w), 1008 (w), 989 (m), 904 (m), 841 (m), 806 (w), 755 (m),

721 (w), 700 (m). UV-vis (CH2Cl2) λmax nm (ε×10-4): 257 (2.10), 329 (0.50), 361 (0.33),

431 (0.20), 493 (0.07), 561 (sh). MS (EI) m/z: 388 (M+), 390 ((M+2)+). Anal. Calcd for

C21H15BrN3: C, 64.79; H, 3.88; N, 10.79. Found: C, 64.40; H, 4.11; N, 10.53.

EPR Spectroscopy. EPR spectra were recorded on a Bruker EMX spectrometer in dilute

deoxygenated CH2Cl2 solution (~10-4 M) using 2,2-diphenyl-1-picrylhydrazyl (DPPH) as

a standard. The spectra were simulated using the WinEPR SimFonia/WINSIM2002

program to give the hyperfine coupling constant with numerical fits (R2 values) of

0.995+. Superhyperfine with multiple hydrogen atoms are not well-resolved (hfcc < 1

Gauss), leading to an overall broadening of the spectrum. Combined with computational

spin densities, the hyperfine coupling constants for radicals were determined, and the spin

densities were calculated using the McConnell equation, with Q(N) = 28.6 G. Kadirov

and Neugebauer 1, 2 analyzed the parent radical 1,3-diphenyl-1,2,4-benzotriazinyl by

ENDOR and concluded that the coupling constants to aromatic hydrogen atoms varied

from aH = 0.23 G to aH = 1.93 G with some degree of error due to the complexity and

difficulty encountered in ENDOR brought about by relaxation of electronic and nuclear

spin systems, as well as the anisotropic character of this radical. In addition, they

concluded that the majority of spin density could be found at N1, with smaller and nearly

equal spin densities on N2 and N4 positions. This suggests that the electronic structure of

the ground state of the radical can best be described by resonance contributors I-III.

ENDOR studies of isotopically labeled 1,3-diphenyl-1,2,4-benzotriazinyl radical suggest

that the electronic structure of the ground state can be best described by a summation of


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resonance structures I – III as shown below in which the largest spin density resides at

N1, with equivalent and smaller spin densities at N2 and N4 due to the contributions of

structures II and III. Computation of the ground state electronic structure of the parent

radical by DFT UB3LYP/6-311G+(d,p) suggests that the largest spin density is at N4

with smaller and equal spin densities at N1 and N2. While it is clear that DFT is not

getting the ground state electronic structure right, it is consistent with the source of the

problem being primarily that the radical has multireference character. Molecules with

low-lying excited or degenerate ground states (such as Jahn-Teller distortions) are

characterized by strong static electron correlation effects that require a multi-

configuration or multi-reference approach for an adequate treatment of the wavefunction.

Some evidence for this is provided by a preliminary CASSCF calculation of the radical

core, in which the spin densities are closer to that found by experiment. The parent

system itself however is too large for proper treatment by CASSCF or CASPT2, and

perhaps might be better treated with some of the newer DFT-CAS or double hybrid/triple

hybrid functionals, which we are in the process of investigating. This however, is work

in progress.

N

NN

N

NN

N

NN

I II III


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Figure 1. X-band EPR spectrum of 1a in CH2Cl2 at 300 K

Figure 2. X-band EPR spectrum of 1b in CH2Cl2 at 300 K

Table 1. Hyperfine coupling constants, spin densities and g-value of 1a and 1b

ρ ρ ρ

Radical a(N1) exp calc

a(N2) exp calc

a(N3) exp calc

g-value

1a 4.76 0.166 0.28 4.99 0.174 0.29 7.47 0.261 0.32 2.0071

1b 4.73 0.165 0.26 5.04 0.176 0.28 7.46 0.261 0.30 2.0065


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Cyclic Voltammetry Measurements. Cyclic voltammetry experiments were performed

with a Bioanalytical Systems CV 50 voltammetric analyzer with a glassy carbon disk as

the working electrode, a Pt wire as the counter electrode, and a Ag wire as a reference

electrode. The analyte solutions in acetonitrile (~1 mM) were placed in electrochemical

cell with 0.1 M Bu4NPF6 as supporting electrolyte. Samples were purged with Ar for 5-

10 min before the data was collected. Peak potentials were referenced to a Standard

Calomel Electrode (SCE) using ferrocene as an internal standard. The redox couple of

ferrocene was taken to be 0.40 V vs SCE in acetonitrile.

Figure 3. Cyclic voltammetry of 1a (right) and 1b (left) in ACN at 300 K with Fc/Fc+ couple (•) as internal standard at a scan rate of 100 mV/s

Table 2. Selected electrochemical parameters of 1a and 1b .

E1/2(ox)/Va ΔEP/mVb E1/2(red)/Vc ΔEP/mVb ΔE/Vd 1a +0.212 60 -0.831 62 1.043 1b +0.249 108 -0.769 104 1.018

aAverage of anodic and cathodic peak potentials corresponding to the oxidation of the

triazinyl radical. bPeak-to-peak separation at a scan rate of 100 mV/s. cAverage of anodic


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and cathodic peak potentials corresponding to the reduction of the triazinyl radical. dΔE = E1/2(ox)-E1/2(red).

Magnetometry Measurements. Magnetization and static magnetic susceptibility

measurements were performed on a Quantum Design MPMS XL-5 system. The static DC

magnetic susceptibility was measured from 2 to 300 K at the field of 1 T on

polycrystalline samples. The contribution of diamagnetic susceptibility was estimated by

slope method and subtracted from the overall magnetic susceptibility. The corrected static

magnetic susceptibility data were fit to the relevant magnetic models by a self-consistent

approximation. For 1a, the diamagnetic contributions were estimated by the slope method

as -4.87×10-4 emu/mol (1a) and 6.96×10-4 emu/mol (1b) by the slope method. ICP-Fe

content measurement reveals Fe content of less than 1 ppm. Measurements were made on

at least 3 independently synthesized and prepared samples in order to assure that the

magnetic behavior observed was not due to the presence of impurities. Magnetic Data Fitting: The static field RSO magnetic susceptibility (χ = M/H) for a

polycrystalline sample of 1a was measured at 10,000 Oe over the temperature range of 2-300 K. Since the radical 1a forms 1D chains via π-π interactions along the b-axis, with interchain interactions, the linear Heisenberg model using the Pade approximant was used to analytically model the temperature dependence of the susceptibility.3

€

χM =Ng2β2

4kBT1+ AK + BK 2 +CK 3 +DK 4 + EK 5

1+ FK +GK 2 +HK 3 + IK 4

⎛

⎝ ⎜

⎞

⎠ ⎟

2 / 3

;

K =J

2kBT

(1)

in which A = 5.7979916, B = 16.902653, C = 29.376885, D = 29.832959, E = 14.036918, F = 2.7979916, G = 7.0086780, H = 8.6538644, I = 4.5743114 with kB = Boltzman constant of 0.695 cm-1 K-1, and J = magnetic exchange coupling constant.

The Weiss approximation was used to account for small magnetic exchange coupling between chains (interchain) leading to an expression for the total calculated magnetic susceptibility as shown below for the expression for χ.


11

Figure 4. Temperature dependence of the magnetic susceptibility χm,p (black) and fit (red)

of a polycrystalline sample of 1a measured at H = 10,000 Oe.

€

χ =Ng2β2

4kB (T −θ)1+ AK + BK 2 +CK 3 +DK 4 + EK 5

1+ FK +GK 2 +HK 3 + IK 4

⎛

⎝ ⎜

⎞

⎠ ⎟

2 / 3

0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

0.04

0 50 100 150 200 250 300

Pade expansion with Weiss constant

! M (e

mu

/ mol

)

T (K)

y = pade(10, 2.0071,-10)ErrorValue

0.0551346.9003a0.052251-3.2516c

NA5.2824e-8ChisqNA1R

fit from 15 - 300 K


12

Figure 5. Temperature dependence of the magnetic moment χm,pT of a polycrystalline sample of 1a measured at H = 10,000 Oe.

Figure 6. Temperature dependence of the magnetic susceptibility χm,p (black) and fit (red) of a polycrystalline sample of 1b measured at H = 10,000 Oe.

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0 50 100 150 200 250 300

Pade fit for Br-3V-DPBT

! M,p

(em

u/m

ol)

T (K)

y = Pade(10, 2.007, -5)ErrorValue

0.215937.3801a0.17509-5.0124c

NA4.8216e-6ChisqNA0.99989R


13

Figure 7. Temperature dependence of the magnetic moment χm,pT of a polycrystalline sample of 1b measured at H = 10,000 Oe.

X-ray Crystallography. Suitable crystals of 1a and 1b were grown from CH2Cl2-

CH3OH solutions of the compounds. Data were collected on a Bruker

PLATFORM/SMART 1000 CCD diffractometer with graphite-monochromated Mo Kα

radiation (λ = 0.71073 Å) at a temperature of -80 °C. Unit cell parameters and

orientation matrices for data collection were determined by least-squares refinement of

2537 reflections with 5.60° < 2θ < 51.18° for 1a, and refinement of 4213 reflections

with 4.64° < 2θ < 48.48° for 1b. The data were corrected for absorption through use

of a multi-‐scan model (SADABS). Structures were solved using direct methods

(SHELXS-97) (1a) or a combined Patterson search/structure expansion method

(DIRDIF-99) (1b). Refinements were completed using the program SHELXL-97.

Hydrogen atoms were assigned positions based on the idealized sp2 geometries of

their attached carbon atoms, and were given thermal parameters 20% greater than


14

those of the attached carbons. The crystallographic data and selected bond lengths and

angles are listed in Tables 3 and 4.

Figure 9. Molecular structure of 1a (left) and 1b (right). Thermal ellipsoids are shown at 50% probability level.

Figure 10. The crystal packing and unit cell of radical 1a.


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Figure 10. The crystal packing and unit cell of radical 1b.


16

Table 3. Crystallographic parameters, bond lengths (Å) and angles (°) for 1a

A. Crystal Data formula C21H16N3 formula weight 310.37 crystal dimensions (mm) 0.80×0.32×0.08 crystal system monoclinic space group I2/a (an alternate setting of C2/c [No. 15]) unit cell parameters a (Å) 26.247 (6) b (Å) 4.9783 (11) c (Å) 26.853 (6) β (deg) 113.635 (4) V (Å3) 3214.5 (13) Z 8 ρcalcd (g cm-‐3) 1.283 µ (mm-‐1) 0.077 B. Data Collection and Refinement Conditions diffractometer Bruker PLATFORM/SMART 1000 CCD radiation (λ[Å]) graphite-‐monochromated Mo Kα (0.71073) temperature (°C) –80 scan type ω scans (0.3°) (20 s exposures) data collection 2θ limit (deg) 51.66 total data collected 11233 (-‐32 ≤ h ≤ 32, -‐6 ≤ k ≤ 6, -‐32 ≤ l ≤ 32) independent reflections 3087 (Rint = 0.0771) number of observed reflections (NO) 1805 [Fo2 ≥ 2σ(Fo2)] structure solution method direct methods (SHELXS–97) refinement method full-‐matrix least-‐squares on F2(SHELXL–97) absorption correction method multi-‐scan (SADABS) range of transmission factors 0.9938–0.9408 data/restraints/parameters 3087 [Fo2 ≥ –3 σ(Fo2)] / 13 / 288 goodness-‐of-‐fit (S) 1.023 [Fo2 ≥ –3 σ( Fo2)] final R indices R1 [Fo2 ≥ 2σ(Fo2)] 0.0594 wR2 [Fo2 ≥ –3σ( Fo2)] 0.1883 largest difference peak and hole 0.312 and –0.381 e Å-‐3


17

C. Bond lengths(Å) and angles(deg)

Atom1 Atom2 Distance N1 N2 1.363(2) N1 C7 1.397(3) N1 C11A 1.457(5)a N1 C11B 1.457(5)a N2 C1 1.336(3) N3 C1 1.340(3) N3 C2 1.366(3) C1 C21 1.486(3) C2 C3 1.405(3) C2 C7 1.416(3) C3 C4 1.370(3) C4 C5 1.399(3) C5 C6 1.382(3) C6 C7 1.394(3) C11A C12A 1.402(12) C11A C16A 1.365(14) C12A C13A 1.397(8) C13A C14A 1.396(12) C14A C15A 1.375(12) C15A C16A 1.383(7) C11B C12B 1.328(18) C11B C16B 1.427(18) C12B C13B 1.384(7) C13B C14B 1.331(14) C14B C15B 1.409(14) C15B C16B 1.391(7) C21 C22 1.394(3) C21 C26 1.389(3) C22 C23 1.386(4) C23 C24 1.391(4) C23 C27 1.491(5) C24 C25 1.385(4) C25 C26 1.384(3) C27 C28A 1.181(5)b C27 C28B 1.169(6)b Atom1 Atom2 Atom3 Angle N2 N1 C7 122.90(18) N2 N1 C11A 115.7(9) N2 N1 C11B 111.8(10) C7 N1 C11A 120.8(9) C7 N1 C11B 124.8(10)


18

N1 N2 C1 116.02(18) C1 N3 C2 116.10(19) N2 C1 N3 127.2(2) N2 C1 C21 115.2(2) N3 C1 C21 117.57(19) N3 C2 C3 119.9(2) N3 C2 C7 122.1(2) C3 C2 C7 118.0(2) C2 C3 C4 121.0(2) C3 C4 C5 120.4(2) C4 C5 C6 120.2(2) C5 C6 C7 119.7(2) N1 C7 C2 115.6(2) N1 C7 C6 123.7(2) C2 C7 C6 120.7(2) N1 C11A C12A 113.6(9) N1 C11A C16A 124.7(9) C12A C11A C16A 121.5(4) C11A C12A C13A 118.2(6) C12A C13A C14A 120.3(7) C13A C14A C15A 119.2(11) C14A C15A C16A 121.4(7) C11A C16A C15A 119.2(5) N1 C11B C12B 124.9(13) N1 C11B C16B 114.0(12) C12B C11B C16B 121.0(4) C11B C12B C13B 120.2(6) C12B C13B C14B 121.5(8) C13B C14B C15B 120.1(11) C14B C15B C16B 119.3(7) C11B C16B C15B 117.9(6) C1 C21 C22 120.0(2) C1 C21 C26 121.5(2) C22 C21 C26 118.6(2) C21 C22 C23 121.9(3) C22 C23 C24 118.3(2) C22 C23 C27 120.3(3) C24 C23 C27 121.5(3) C23 C24 C25 120.8(3) C24 C25 C26 120.0(3) C21 C26 C25 120.4(2) C23 C27 C28A 136.2(5)c C23 C27 C28B 135.4(6)c aThe N1–C11A and N1–C11B distances were constrained to be equal (within 0.01 Å) during refinement. bThe C27–C28A and C27–C28B distances were constrained to be


19

equal (within 0.02 Å) during refinement. cThe C23…C28A and C23…C28B distances were constrained to be equal (within 0.02 Å) during refinement Table 4. Crystallographic parameters, bond lengths (Å) and angles (°) for 1b A. Crystal Data formula C21H15BrN3 formula weight 389.27 crystal dimensions (mm) 0.51×0.28×0.27 crystal system monoclinic space group P21/n (an alternate setting of P21/c [No. 14]) unit cell parameters a (Å) 16.5376 (18) b (Å) 13.7569 (15) c (Å) 22.820 (3) β (deg) 93.7888 (18) V (Å3) 5180.3 (10) Z 12 ρcalcd (g cm-‐3) 1.497 µ (mm-‐1) 2.388 B. Data Collection and Refinement Conditions diffractometer Bruker PLATFORM/SMART 1000 CCD radiation (λ[Å]) graphite-‐monochromated Mo Kα (0.71073) temperature (°C) –80 scan type ω scans (0.3°) (20 s exposures) data collection 2θ limit (deg) 50.00 total data collected 35190 (-‐19 ≤ h ≤ 19, -‐16 ≤ k ≤ 16, -‐27 ≤ l ≤ 27) independent reflections 9135 (Rint = 0.0514) number of observed reflections (NO) 6107 [Fo2 ≥ 2σ(Fo2)] structure solution method Patterson search/structure expansion (DIRDIF–99) refinement method full-‐matrix least-‐squares on F2(SHELXL–97) absorption correction method multi-‐scan (SADABS) range of transmission factors 0.5649–0.3755 data/restraints/parameters 9135 [Fo2 ≥ –3σ(Fo2)] / 0 / 676 goodness-‐of-‐fit (S) 1.005 [Fo2 ≥ –3σ( Fo2)] final R indices R1 [Fo2 ≥ 2σ(Fo2)] 0.0425 wR2 [Fo2 ≥ –3σ( Fo2)] 0.1198 largest difference peak and hole 1.125 and –0.411 e Å-‐3


20

C. Bond lengths(Å) and angles(deg)

Molecule A

Atom1 Atom2 Distance Br1 C14 1.895(4) N1 N2 1.368(4) N1 C7 1.392(4) N1 C11 1.426(4) N2 C1 1.336(4) N3 C1 1.331(4) N3 C2 1.372(4) C1 C21 1.490(5) C2 C3 1.406(5) C2 C7 1.408(5) C3 C4 1.371(5) C4 C5 1.384(5) C5 C6 1.377(5) C6 C7 1.396(5) C11 C12 1.388(5) C11 C16 1.383(5) C12 C13 1.381(5) C13 C14 1.364(5) C14 C15 1.379(5) C15 C16 1.383(5) C21 C22 1.385(5) C21 C26 1.386(5) C22 C23 1.392(5) C23 C24 1.392(5) C23 C27 1.487(6) C24 C25 1.374(6) C25 C26 1.389(5) C27 C28 1.236(6) Atom1 Atom2 Atom3 Angle N2 N1 C7 122.3(3) N2 N1 C11 113.7(3) C7 N1 C11 123.8(3) N1 N2 C1 115.8(3) C1 N3 C2 115.2(3) N2 C1 N3 128.0(3) N2 C1 C21 115.0(3) N3 C1 C21 117.0(3) N3 C2 C3 118.9(3) N3 C2 C7 122.6(3)


21

C3 C2 C7 118.5(3) C2 C3 C4 120.3(3) C3 C4 C5 120.6(3) C4 C5 C6 120.8(4) C5 C6 C7 119.4(3) N1 C7 C2 115.9(3) N1 C7 C6 123.7(3) C2 C7 C6 120.4(3) N1 C11 C12 119.0(3) N1 C11 C16 121.7(3) C12 C11 C16 119.2(3) C11 C12 C13 120.3(3) C12 C13 C14 119.4(3) Br1 C14 C13 119.2(3) Br1 C14 C15 119.1(3) C13 C14 C15 121.7(3) C14 C15 C16 118.7(3) C11 C16 C15 120.7(3) C1 C21 C22 119.1(3) C1 C21 C26 121.8(3) C22 C21 C26 119.1(3) C21 C22 C23 121.9(3) C22 C23 C24 117.9(4) C22 C23 C27 119.3(4) C24 C23 C27 122.8(4) C23 C24 C25 120.8(4) C24 C25 C26 120.7(4) C21 C26 C25 119.6(4) C23 C27 C28 129.1(5)

Molecule B

Atom1 Atom2 Distance Br1 C14 1.895(3) N1 N2 1.374(4) N1 C7 1.397(4) N1 C11 1.420(4) N2 C1 1.336(4) N3 C1 1.337(4) N3 C2 1.372(4) C1 C21 1.492(5) C2 C3 1.411(5) C2 C7 1.409(5) C3 C4 1.369(5) C4 C5 1.378(5) C5 C6 1.385(5)


22

C6 C7 1.395(5) C11 C12 1.383(5) C11 C16 1.382(5) C12 C13 1.376(5) C13 C14 1.377(5) C14 C15 1.380(5) C15 C16 1.377(5) C21 C22 1.387(5) C21 C26 1.385(5) C22 C23 1.393(5) C23 C24 1.395(6) C23 C27 1.468(6) C24 C25 1.366(6) C25 C26 1.396(5) C27 C28 1.181(8)

Atom1 Atom2 Atom3 Angle N2 N1 C7 122.1(3) N2 N1 C11 114.0(3) C7 N1 C11 123.9(3) N1 N2 C1 115.9(3) C1 N3 C2 115.4(3) N2 C1 N3 127.7(3) N2 C1 C21 114.7(3) N3 C1 C21 117.6(3) N3 C2 C3 119.4(3) N3 C2 C7 122.5(3) C3 C2 C7 118.1(3) C2 C3 C4 120.6(3) C3 C4 C5 120.7(3) C4 C5 C6 120.6(4) C5 C6 C7 119.4(4) N1 C7 C2 115.9(3) N1 C7 C6 123.6(3) C2 C7 C6 120.5(3) N1 C11 C12 120.0(3) N1 C11 C16 120.3(3) C12 C11 C16 119.6(3) C11 C12 C13 120.1(3) C12 C13 C14 119.7(3) Br1 C14 C13 120.1(3) Br1 C14 C15 119.1(3) C13 C14 C15 120.8(3) C14 C15 C16 119.1(3) C11 C16 C15 120.6(3) C1 C21 C22 120.1(3)


23

C1 C21 C26 120.5(3) C22 C21 C26 119.5(3) C21 C22 C23 121.4(4) C22 C23 C24 118.0(4) C22 C23 C27 123.6(5) C24 C23 C27 118.4(4) C23 C24 C25 120.9(4) C24 C25 C26 120.7(4) C21 C26 C25 119.3(4) C23 C27 C28 129.1(7)

Molecule C

Atom1 Atom2 Distance Br1 C14 1.898(4) N1 N2 1.367(4) N1 C7 1.388(4) N1 C11 1.433(4) N2 C1 1.337(4) N3 C1 1.340(4) N3 C2 1.375(4) C1 C21 1.482(5) C2 C3 1.402(5) C2 C7 1.406(5) C3 C4 1.379(5) C4 C5 1.380(5) C5 C6 1.383(5) C6 C7 1.402(5) C11 C12 1.385(5) C11 C16 1.389(5) C12 C13 1.381(5) C13 C14 1.377(5) C14 C15 1.387(5) C15 C16 1.372(5) C21 C22 1.384(5) C21 C26 1.392(5) C22 C23 1.399(5) C23 C24 1.400(6) C23 C27 1.463(6) C24 C25 1.373(6) C25 C26 1.381(5) C27 C28 1.183(8) Atom1 Atom2 Atom3 Angle N2 N1 C7 122.1(3) N2 N1 C11 113.3(3)


24

C7 N1 C11 123.7(3) N1 N2 C1 116.4(3) C1 N3 C2 115.9(3) N2 C1 N3 126.8(3) N2 C1 C21 115.2(3) N3 C1 C21 117.9(3) N3 C2 C3 119.2(3) N3 C2 C7 121.9(3) C3 C2 C7 118.9(3) C2 C3 C4 120.5(3) C3 C4 C5 120.0(3) C4 C5 C6 121.2(4) C5 C6 C7 119.2(3) N1 C7 C2 116.5(3) N1 C7 C6 123.4(3) C2 C7 C6 120.1(3) N1 C11 C12 118.9(3) N1 C11 C16 121.2(3) C12 C11 C16 119.9(3) C11 C12 C13 120.1(3) C12 C13 C14 119.3(3) Br1 C14 C13 118.8(3) Br1 C14 C15 120.1(3) C13 C14 C15 121.1(3) C14 C15 C16 119.3(3) C11 C16 C15 120.3(3) C1 C21 C22 120.0(3) C1 C21 C26 120.9(3) C22 C21 C26 119.0(3) C21 C22 C23 121.4(4) C22 C23 C24 118.1(4) C22 C23 C27 123.2(4) C24 C23 C27 118.6(4) C23 C24 C25 120.6(4) C24 C25 C26 120.6(4) C21 C26 C25 120.2(4) C23 C27 C28 129.0(6)


25

Computations:

Figure 12. α-HOMO (SOMO)(left) and SCF spin density (right) of radical 1a (DFT UB3LYP/6-31G(d,p)) generated with Gaussview03

Figure 13. α-HOMO (SOMO) (left) and SCF spin density (right) of radical 1b (DFT UB3LYP/6-31G(d,p)) generated with Gaussview03.


26

Table 5. Computational output parameters for 1a (Monomer, UB3LYP doublet state)

1\1\GINC-COMPUTE-0-20\SP\UB3LYP\6-311+G(d,p)\C21H16N3(2)\BRYNND\26-Aug -2010\0\\#ub3lyp/6-311+g(d,p)\\082510_3V-DPBTmono_doublet_ub3lyp_6311 +gdp\\0,2\N\N,1,1.36254211\N,2,2.396681,1,89.58117239\C,2,1.33588458,1 ,116.02142804,3,0.26780755,0\C,3,1.36587082,2,89.75295307,1,0.68126229 ,0\C,5,1.40476922,3,119.85523361,2,-179.63420156,0\H,6,0.94959519,5,11 9.53818189,3,-0.29946733,0\C,6,1.36968251,5,121.00297327,3,179.7240992 8,0\H,8,0.94977895,6,119.82236013,5,-179.40837525,0\C,8,1.39941961,6,1 20.38903251,5,0.54820037,0\H,10,0.95098857,8,119.8788303,6,179.0676949 4,0\C,10,1.38198678,8,120.20589249,6,-0.84930298,0\H,12,0.9501185,10,1 20.09936877,8,-179.65634917,0\C,12,1.39438974,10,119.6911532,8,0.40327 736,0\C,1,1.45683334,2,115.54922464,4,-171.45318757,0\C,15,1.40012785, 1,113.62225358,2,-69.36241313,0\H,16,0.94951938,15,120.84162156,1,2.40 185602,0\C,16,1.39716631,15,118.27411153,1,-177.72746348,0\H,18,0.9507 9754,16,119.83683381,15,179.54407404,0\C,18,1.39594368,16,120.32343371 ,15,-0.58842164,0\H,20,0.94907728,18,120.41144521,16,-177.0162067,0\C, 20,1.37480908,18,119.19493785,16,3.32038935,0\H,22,0.95004742,20,119.2 2701881,18,178.08295923,0\C,15,1.36566756,1,124.65003475,2,116.6906292 ,0\H,24,0.94981457,15,120.36114103,1,-1.71496227,0\C,4,1.48549508,2,11 5.21978177,1,-179.62406156,0\C,26,1.39400832,4,119.94143452,2,171.5852 237,0\H,27,0.95104379,26,119.06794236,4,-0.50252495,0\C,27,1.38619636, 26,121.83286448,4,179.44468324,0\C,29,1.39064844,27,118.28785541,26,0. 03883361,0\H,30,0.95074725,29,119.6079299,27,-179.35047431,0\C,30,1.38 521268,29,120.80710273,27,0.67826058,0\H,32,0.95082571,30,120.04624125 ,29,178.9119542,0\C,32,1.38406895,30,120.03464915,29,-1.09674094,0\H,3 4,0.95062689,32,119.80470857,30,-179.18978346,0\C,29,1.49123923,27,120 .24843824,26,-179.95302895,0\H,36,0.95001597,29,111.89705667,27,-11.15 409784,0\C,36,1.18159163,29,136.27590649,27,168.79631045,0\H,38,0.9495 6966,36,122.91854983,29,-179.95122101,0\H,38,0.95140125,36,117.2311584 4,29,-0.02460336,0\\Version=AM64L-G09RevA.02\State=2-A\HF=-974.0285209 \S2=0.766024\S2-1=0.\S2A=0.750149\RMSD=2.563e-09\Dipole=-0.8087534,0.0 576545,-1.1872815\Quadrupole=3.6270961,-8.70588,5.0787839,-0.4264948,3 .0853455,-2.2640711\PG=C01 [X(C21H16N3)]\\@

Table 6. Computational output parameters for 1a (Dimer, UB3LYP singlet state)

1\1\GINC-COMPUTE-0-20\SP\UB3LYP\6-311+G(d,p)\C42H32N6\BRYNND\25-Aug-20 10\0\\# ub3lyp/6-311+g(d,p) guess=mix\\082510_3V-DPBT_singlet_ub3lyp_6 311+gdp\\0,1\N,0,1.2374,0.7901,8.6754\N,0,1.5503,1.7329,7.7428\N,0,-0. 4708,1.2127,6.5644\C,0,0.6718,1.8878,6.7484\C,0,-0.779,0.2823,7.5157\C ,0,-1.9616,-0.4675,7.4033\H,0,-2.5421,-0.3186,6.6667\C,0,-2.2909,-1.41 04,8.3406\H,0,-3.0905,-1.9137,8.2436\C,0,-1.4556,-1.6374,9.4402\H,0,-1 .6979,-2.2845,10.0936\C,0,-0.2809,-0.923,9.5802\H,0,0.2875,-1.0818,10. 3248\C,0,0.0648,0.0319,8.6247\C,0,2.0953,0.7617,9.8525\C,0,3.3942,0.31 01,9.5893\H,0,3.6626,0.0876,8.7061\C,0,4.2855,0.1981,10.6594\H,0,5.171 1,-0.1125,10.5069\C,0,3.883,0.5426,11.9509\H,0,4.4994,0.5073,12.6717\C ,0,2.5809,0.927,12.1674\H,0,2.2994,1.1351,13.0506\C,0,1.6749,1.0191,11


27

.1261\H,0,0.7715,1.2595,11.2941\C,0,1.0347,2.9138,5.7373\C,0,0.2836,3. 0358,4.5693\H,0,-0.4533,2.4508,4.4306\C,0,0.5803,3.9866,3.6052\C,0,1.6 612,4.8334,3.8254\H,0,1.8758,5.4985,3.1808\C,0,2.4296,4.7194,4.9723\H, 0,3.1756,5.2939,5.1046\C,0,2.1122,3.7691,5.9272\H,0,2.6348,3.7014,6.71 84\C,0,-0.2477,4.0867,2.369\H,0,-0.8357,3.3464,2.2755\C,0,-0.3598,4.85 23,1.476\H,0,-0.9705,4.7244,0.7602\H,0,0.1943,5.6255,1.4933\N,0,1.2374 ,5.7684,8.6754\N,0,1.5503,6.7112,7.7428\N,0,-0.4708,6.191,6.5644\C,0,0 .6718,6.8661,6.7484\C,0,-0.779,5.2606,7.5157\C,0,-1.9616,4.5108,7.4033 \H,0,-2.5421,4.6597,6.6667\C,0,-2.2909,3.5679,8.3406\H,0,-3.0905,3.064 6,8.2436\C,0,-1.4556,3.3409,9.4402\H,0,-1.6979,2.6938,10.0936\C,0,-0.2 809,4.0553,9.5802\H,0,0.2875,3.8965,10.3248\C,0,0.0648,5.0102,8.6247\C ,0,2.0953,5.74,9.8525\C,0,3.3942,5.2884,9.5893\H,0,3.6626,5.0659,8.706 1\C,0,4.2855,5.1764,10.6594\H,0,5.1711,4.8658,10.5069\C,0,3.883,5.5209 ,11.9509\H,0,4.4994,5.4856,12.6717\C,0,2.5809,5.9053,12.1674\H,0,2.299 4,6.1134,13.0506\C,0,1.6749,5.9974,11.1261\H,0,0.7715,6.2378,11.2941\C ,0,1.0347,7.8921,5.7373\C,0,0.2836,8.0141,4.5693\H,0,-0.4533,7.4291,4. 4306\C,0,0.5803,8.9649,3.6052\C,0,1.6612,9.8117,3.8254\H,0,1.8758,10.4 768,3.1808\C,0,2.4296,9.6977,4.9723\H,0,3.1756,10.2722,5.1046\C,0,2.11 22,8.7474,5.9272\H,0,2.6348,8.6797,6.7184\C,0,-0.2477,9.065,2.369\H,0, -0.8357,8.3247,2.2755\C,0,-0.3598,9.8306,1.476\H,0,-0.9705,9.7027,0.76 02\H,0,0.1943,10.6038,1.4933\\Version=AM64L-G09RevA.02\State=1-A\HF=-1 948.0502997\S2=1.032279\S2-1=0.\S2A=0.262138\RMSD=1.215e-09\Dipole=0.6 763809,-1.1690203,2.2004786\Quadrupole=0.522481,-9.5488208,9.0263399,5 .2559364,7.2126708,-10.2416474\PG=C01 [X(C42H32N6)]\\@

Table 7. Computational output parameters for 1a (Dimer, UB3LYP triplet state)

1\1\GINC-COMPUTE-0-19\SP\UB3LYP\6-311+G(d,p)\C42H32N6(3)\BRYNND\25-Aug -2010\0\\# ub3lyp/6-311+g(d,p)\\082510_3V-DPBT_triplet_ub3lyp_6311+gdp \\0,3\N,0,1.2374,0.7901,8.6754\N,0,1.5503,1.7329,7.7428\N,0,-0.4708,1. 2127,6.5644\C,0,0.6718,1.8878,6.7484\C,0,-0.779,0.2823,7.5157\C,0,-1.9 616,-0.4675,7.4033\H,0,-2.5421,-0.3186,6.6667\C,0,-2.2909,-1.4104,8.34 06\H,0,-3.0905,-1.9137,8.2436\C,0,-1.4556,-1.6374,9.4402\H,0,-1.6979,- 2.2845,10.0936\C,0,-0.2809,-0.923,9.5802\H,0,0.2875,-1.0818,10.3248\C, 0,0.0648,0.0319,8.6247\C,0,2.0953,0.7617,9.8525\C,0,3.3942,0.3101,9.58 93\H,0,3.6626,0.0876,8.7061\C,0,4.2855,0.1981,10.6594\H,0,5.1711,-0.11 25,10.5069\C,0,3.883,0.5426,11.9509\H,0,4.4994,0.5073,12.6717\C,0,2.58 09,0.927,12.1674\H,0,2.2994,1.1351,13.0506\C,0,1.6749,1.0191,11.1261\H ,0,0.7715,1.2595,11.2941\C,0,1.0347,2.9138,5.7373\C,0,0.2836,3.0358,4. 5693\H,0,-0.4533,2.4508,4.4306\C,0,0.5803,3.9866,3.6052\C,0,1.6612,4.8 334,3.8254\H,0,1.8758,5.4985,3.1808\C,0,2.4296,4.7194,4.9723\H,0,3.175 6,5.2939,5.1046\C,0,2.1122,3.7691,5.9272\H,0,2.6348,3.7014,6.7184\C,0, -0.2477,4.0867,2.369\H,0,-0.8357,3.3464,2.2755\C,0,-0.3598,4.8523,1.47 6\H,0,-0.9705,4.7244,0.7602\H,0,0.1943,5.6255,1.4933\N,0,1.2374,5.7684 ,8.6754\N,0,1.5503,6.7112,7.7428\N,0,-0.4708,6.191,6.5644\C,0,0.6718,6 .8661,6.7484\C,0,-0.779,5.2606,7.5157\C,0,-1.9616,4.5108,7.4033\H,0,-2 .5421,4.6597,6.6667\C,0,-2.2909,3.5679,8.3406\H,0,-3.0905,3.0646,8.243 6\C,0,-1.4556,3.3409,9.4402\H,0,-1.6979,2.6938,10.0936\C,0,-0.2809,4.0 553,9.5802\H,0,0.2875,3.8965,10.3248\C,0,0.0648,5.0102,8.6247\C,0,2.09


28

53,5.74,9.8525\C,0,3.3942,5.2884,9.5893\H,0,3.6626,5.0659,8.7061\C,0,4 .2855,5.1764,10.6594\H,0,5.1711,4.8658,10.5069\C,0,3.883,5.5209,11.950 9\H,0,4.4994,5.4856,12.6717\C,0,2.5809,5.9053,12.1674\H,0,2.2994,6.113 4,13.0506\C,0,1.6749,5.9974,11.1261\H,0,0.7715,6.2378,11.2941\C,0,1.03 47,7.8921,5.7373\C,0,0.2836,8.0141,4.5693\H,0,-0.4533,7.4291,4.4306\C, 0,0.5803,8.9649,3.6052\C,0,1.6612,9.8117,3.8254\H,0,1.8758,10.4768,3.1 808\C,0,2.4296,9.6977,4.9723\H,0,3.1756,10.2722,5.1046\C,0,2.1122,8.74 74,5.9272\H,0,2.6348,8.6797,6.7184\C,0,-0.2477,9.065,2.369\H,0,-0.8357 ,8.3247,2.2755\C,0,-0.3598,9.8306,1.476\H,0,-0.9705,9.7027,0.7602\H,0, 0.1943,10.6038,1.4933\\Version=AM64L-G09RevA.02\State=3-A\HF=-1948.050 3227\S2=2.032622\S2-1=0.\S2A=2.000615\RMSD=2.113e-09\Dipole=0.6755764, -1.1707188,2.2003305\Quadrupole=0.5185149,-9.5360679,9.0175529,5.26516 95,7.2118931,-10.242479\PG=C01 [X(C42H32N6)]\\@

Table 8. Computational output parameters for 1a (Dimer, UM052-X singlet state)

1\1\GINC-COMPUTE-0-2\SP\UM052X\6-311+G(d,p)\C42H32N6\BRYNND\08-Sep-201 0\0\\# 6-311+g(d,p) guess=mix um052x\\090710_3V-DPBT_singlet_um052x_63 11+gdp\\0,1\N,0,3.301332,-0.94204,-0.780402\N,0,1.998406,-0.793606,-1. 150366\N,0,1.492284,-2.913816,-0.154057\C,0,1.174988,-1.788254,-0.8079 57\C,0,2.79851,-3.041175,0.224305\C,0,3.216628,-4.188201,0.919204\H,0, 2.585232,-4.866891,1.125236\C,0,4.521753,-4.342803,1.304922\H,0,4.7878 71,-5.128988,1.766631\C,0,5.465991,-3.349467,1.021949\H,0,6.367397,-3. 458322,1.304787\C,0,5.092136,-2.210415,0.334432\H,0,5.73551,-1.53919,0 .138852\C,0,3.766994,-2.05098,-0.069178\C,0,4.149034,0.225234,-0.98346 8\C,0,4.391321,0.514945,-2.331697\H,0,3.992203,-0.002945,-3.020233\C,0 ,5.233201,1.587295,-2.637276\H,0,5.418173,1.799633,-3.545413\C,0,5.801 883,2.350164,-1.61586\H,0,6.339806,3.104393,-1.822078\C,0,5.579033,1.9 91595,-0.307477\H,0,5.988174,2.494021,0.387334\C,0,4.77018,0.917223,0. 016721\H,0,4.64701,0.664084,0.923858\C,0,-0.239087,-1.612177,-1.227582 \C,0,-1.144654,-2.661575,-1.079349\H,0,-0.841023,-3.485923,-0.715012\C ,0,-2.475293,-2.536509,-1.447178\C,0,-2.901163,-1.323676,-1.977815\H,0 ,-3.811912,-1.214238,-2.227773\C,0,-2.014471,-0.273022,-2.147276\H,0,- 2.313905,0.54636,-2.52546\C,0,-0.691495,-0.4147,-1.76608\H,0,-0.088454 ,0.312323,-1.873183\C,0,-3.413931,-3.681978,-1.272095\H,0,-2.955224,-4 .487053,-1.062395\C,0,-4.58308,-3.843982,-1.3269\H,0,-4.994981,-4.6861 72,-1.176118\H,0,-5.118673,-3.084733,-1.53146\N,0,-0.43207,1.928814,0. 833096\N,0,-1.734995,2.077248,0.463132\N,0,-2.241117,-0.042961,1.45944 2\C,0,-2.558414,1.0826,0.805541\C,0,-0.934892,-0.170321,1.837803\C,0,- 0.516773,-1.317347,2.532703\H,0,-1.14817,-1.996037,2.738735\C,0,0.7883 51,-1.471949,2.918421\H,0,1.054469,-2.258133,3.38013\C,0,1.732589,-0.4 78613,2.635448\H,0,2.633995,-0.587468,2.918286\C,0,1.358734,0.660439,1 .947931\H,0,2.002109,1.331664,1.752351\C,0,0.033592,0.819874,1.544321\ C,0,0.415632,3.096088,0.630031\C,0,0.657919,3.3858,-0.718199\H,0,0.258 801,2.867909,-1.406734\C,0,1.4998,4.458149,-1.023777\H,0,1.684771,4.67 0487,-1.931915\C,0,2.068481,5.221019,-0.002361\H,0,2.606404,5.975247,- 0.208579\C,0,1.845632,4.862449,1.306022\H,0,2.254772,5.364875,2.000833 \C,0,1.036778,3.788077,1.630219\H,0,0.913609,3.534939,2.537357\C,0,-3. 972489,1.258677,0.385916\C,0,-4.878056,0.20928,0.534149\H,0,-4.574424, -0.615069,0.898486\C,0,-6.208695,0.334346,0.166321\C,0,-6.634564,1.547 178,-0.364316\H,0,-7.545314,1.656616,-0.614274\C,0,-5.747872,2.597833, -0.533777\H,0,-6.047307,3.417214,-0.911961\C,0,-4.424897,2.456155,-0.1


29

52582\H,0,-3.821855,3.183177,-0.259684\C,0,-7.147332,-0.811124,0.34140 3\H,0,-6.688626,-1.616198,0.551103\C,0,-8.316482,-0.973128,0.286598\H, 0,-8.728383,-1.815318,0.437381\H,0,-8.852075,-0.213879,0.082038\\Versi on=AM64L-G09RevA.02\State=1-A\HF=-1947.8673802\S2=1.052114\S2-1=0.\S2A =0.421909\RMSD=7.504e-10\Dipole=2.4404021,1.0288459,0.0545294\Quadrupo le=10.3225994,1.5618579,-11.8844573,10.3099298,6.6176591,-9.0258605\PG =C01 [X(C42H32N6)]\\@

Table 9. Computational output parameters for 1a (Dimer, UM052-X triplet state)

1\1\GINC-COMPUTE-0-9\SP\UM052X\6-311+G(d,p)\C42H32N6(3)\BRYNND\08-Sep- 2010\0\\# 6-311+g(d,p) um052x\\090710_3V-DPBT_triplet_um052x_6311+gdp\ \0,3\N,0,3.301332,-0.94204,-0.780402\N,0,1.998406,-0.793606,-1.150366\ N,0,1.492284,-2.913816,-0.154057\C,0,1.174988,-1.788254,-0.807957\C,0, 2.79851,-3.041175,0.224305\C,0,3.216628,-4.188201,0.919204\H,0,2.58523 2,-4.866891,1.125236\C,0,4.521753,-4.342803,1.304922\H,0,4.787871,-5.1 28988,1.766631\C,0,5.465991,-3.349467,1.021949\H,0,6.367397,-3.458322, 1.304787\C,0,5.092136,-2.210415,0.334432\H,0,5.73551,-1.53919,0.138852 \C,0,3.766994,-2.05098,-0.069178\C,0,4.149034,0.225234,-0.983468\C,0,4 .391321,0.514945,-2.331697\H,0,3.992203,-0.002945,-3.020233\C,0,5.2332 01,1.587295,-2.637276\H,0,5.418173,1.799633,-3.545413\C,0,5.801883,2.3 50164,-1.61586\H,0,6.339806,3.104393,-1.822078\C,0,5.579033,1.991595,- 0.307477\H,0,5.988174,2.494021,0.387334\C,0,4.77018,0.917223,0.016721\ H,0,4.64701,0.664084,0.923858\C,0,-0.239087,-1.612177,-1.227582\C,0,-1 .144654,-2.661575,-1.079349\H,0,-0.841023,-3.485923,-0.715012\C,0,-2.4 75293,-2.536509,-1.447178\C,0,-2.901163,-1.323676,-1.977815\H,0,-3.811 912,-1.214238,-2.227773\C,0,-2.014471,-0.273022,-2.147276\H,0,-2.31390 5,0.54636,-2.52546\C,0,-0.691495,-0.4147,-1.76608\H,0,-0.088454,0.3123 23,-1.873183\C,0,-3.413931,-3.681978,-1.272095\H,0,-2.955224,-4.487053 ,-1.062395\C,0,-4.58308,-3.843982,-1.3269\H,0,-4.994981,-4.686172,-1.1 76118\H,0,-5.118673,-3.084733,-1.53146\N,0,-0.43207,1.928814,0.833096\ N,0,-1.734995,2.077248,0.463132\N,0,-2.241117,-0.042961,1.459442\C,0,- 2.558414,1.0826,0.805541\C,0,-0.934892,-0.170321,1.837803\C,0,-0.51677 3,-1.317347,2.532703\H,0,-1.14817,-1.996037,2.738735\C,0,0.788351,-1.4 71949,2.918421\H,0,1.054469,-2.258133,3.38013\C,0,1.732589,-0.478613,2 .635448\H,0,2.633995,-0.587468,2.918286\C,0,1.358734,0.660439,1.947931 \H,0,2.002109,1.331664,1.752351\C,0,0.033592,0.819874,1.544321\C,0,0.4 15632,3.096088,0.630031\C,0,0.657919,3.3858,-0.718199\H,0,0.258801,2.8 67909,-1.406734\C,0,1.4998,4.458149,-1.023777\H,0,1.684771,4.670487,-1 .931915\C,0,2.068481,5.221019,-0.002361\H,0,2.606404,5.975247,-0.20857 9\C,0,1.845632,4.862449,1.306022\H,0,2.254772,5.364875,2.000833\C,0,1. 036778,3.788077,1.630219\H,0,0.913609,3.534939,2.537357\C,0,-3.972489, 1.258677,0.385916\C,0,-4.878056,0.20928,0.534149\H,0,-4.574424,-0.6150 69,0.898486\C,0,-6.208695,0.334346,0.166321\C,0,-6.634564,1.547178,-0. 364316\H,0,-7.545314,1.656616,-0.614274\C,0,-5.747872,2.597833,-0.5337 77\H,0,-6.047307,3.417214,-0.911961\C,0,-4.424897,2.456155,-0.152582\H ,0,-3.821855,3.183177,-0.259684\C,0,-7.147332,-0.811124,0.341403\H,0,- 6.688626,-1.616198,0.551103\C,0,-8.316482,-0.973128,0.286598\H,0,-8.72 8383,-1.815318,0.437381\H,0,-8.852075,-0.213879,0.082038\\Version=AM64 L-G09RevA.02\State=3-A\HF=-1947.8674074\S2=2.052472\S2-1=0.\S2A=2.0015 97\RMSD=4.165e-09\Dipole=2.4411412,1.0274885,0.0548044\Quadrupole=10.3 246826,1.5669393,-11.8916219,10.2966044,6.6177187,-9.0269291\PG=C01 [X


30

(C42H32N6)]\\@

Table 10. Computational output parameters for 1b 1|1|UNPC-UNK|SP|UB3LYP|6-31G(d,p)|C21H15Br1N3(2)|PCUSER|12-Jul-2009|0| |# UB3LYP/6-31G(D,P) GUESS=SAVE GEOM=CONNECTIVITY||vic0626||0,2|Br|N,1 ,6.07113931|N,2,1.36811277,1,112.13395182|N,3,2.39660491,2,89.88351712 ,1,-179.65557913,0|C,4,1.33058709,3,26.03641739,2,-179.46777007,0|C,4, 1.3728322,3,89.11546093,2,-2.47759275,0|C,6,1.40640437,4,118.8695118,3 ,-178.52532496,0|H,7,0.94970671,6,119.82395161,4,-3.46669027,0|C,7,1.3 7069318,6,120.25327366,4,176.55980066,0|H,9,0.94949786,7,119.73628448, 6,-179.8552308,0|C,9,1.38431652,7,120.56049218,6,0.29255272,0|H,11,0.9 5061876,9,119.54852477,7,-178.67235398,0|C,11,1.37620079,9,120.8086242 3,7,1.22869866,0|H,13,0.95061363,11,120.34870058,9,179.35356964,0|C,2, 1.39283783,1,125.42554372,3,176.0285277,0|C,2,1.42611405,1,1.59089071, 3,-179.08967501,0|C,16,1.38810585,2,119.01247099,1,-43.46445756,0|H,17 ,0.95026288,16,119.91393932,2,-1.6002426,0|C,17,1.38109163,16,120.2939 6461,2,178.40776665,0|H,19,0.9505303,17,120.25103649,16,179.41583788,0 |C,19,1.36265009,17,119.36396142,16,-0.58676397,0|C,21,1.37885023,19,1 21.74276513,17,-1.0444102,0|H,22,0.94991003,21,120.65780974,19,-178.57 582654,0|C,22,1.38205893,21,118.66291596,19,1.4072412,0|H,24,0.9506301 1,22,119.62450688,21,179.91829541,0|C,5,1.49045438,4,116.97498275,3,-1 78.70476449,0|C,26,1.3845822,5,119.10524366,4,-13.06007341,0|H,27,0.95 148128,26,119.04884553,5,0.13508206,0|C,27,1.39224864,26,121.96729015, 5,-179.81263587,0|C,29,1.39124673,27,117.82036776,26,-1.11396702,0|H,3 0,0.94943656,29,119.53160693,27,-179.08565725,0|C,30,1.37458958,29,120 .77677334,27,0.86265862,0|H,32,0.95014134,30,119.64281051,29,-179.4876 1948,0|C,26,1.3861375,5,121.76413678,4,167.1376507,0|H,34,0.94902839,2 6,120.26320559,5,1.12842636,0|C,29,1.48755682,27,119.34140971,26,177.7 3700847,0|H,36,0.95137204,29,115.42427031,27,-2.46998693,0|C,36,1.2347 0984,29,129.13879483,27,177.51119873,0|H,38,0.95029774,36,120.05328136 ,29,0.05537946,0|H,38,0.94981531,36,120.06089524,29,-179.96582185,0||V ersion=x86-Win32-G03RevB.04|State=2-A|HF=-3544.948861|S2=0.761249|S2-1 =0.|S2A=0.750078|RMSD=5.564e-005|Dipole=-0.7404745,0.0852041,-0.175104 9|PG=C01 [X(C21H15Br1N3)]||@


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Supplementary Information - Royal Society of Chemistry · 1! Supplementary Information...

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