Kirill I. Sinyushin, Ivan S. Golovanov, Pavel Yu. Ushakov, Vladislav K. Lesnikov, Yulia V. Nelyubina, Alexey Yu. Sukhorukov. “Unlocking coordination chemistry and photocatalytic activity of Mn(IV) complexes with 1,4,6,10-tetraazaadamantane-based tris-hydroxylamine ligand TAAD.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15001876/v2

[Mn(TAAD)(tacn)]Cl
Identifier C1
Mp above 210 °C
FT-IR (KBr) 3262 (br), 2929 (s), 1641 (m,br), 1500 (w), 1455 (s), 1432 (s), 1375 (s), 1324 (m), 1262 (w), 1262 (s), 1213 (m), 1177 (m), 1100 (s), 1075 (m), 1028 (s), 972 (s), 951 (s), 871 (m), 820 (s), 795 (s), 747 (m), 703 (s), 627 (s), 649 (s), 608 (m), 584 (m), 540 (s), 511 (s), 469 (m), 415 (s)
UV–vis spectrum (MeOH, c = 3.4 × 10⁻⁴ M) peaks λ nm: 298, 459, 548
UV–vis spectrum (MeCN, c = 2.5 × 10⁻⁴ M) peaks λ nm: 295, 462, 545
ESI-HRMS m/z [C1-Cl]⁺ Calcd for [C₁₅H₃₀MnN₇O₃]⁺ 411.1785; Found 411.1780
Elemental analysis Calcd for C₁₅H₃₀ClMnN₇O₃·CH₃OH·2H₂O: C, 37.32; H, 7.44; N, 19.04. Found: C, 37.35; H, 6.52; N, 19.32
SI, p. S4
Mn(TAAD)(phen)Cl
Identifier C2
Mp above 210 °C
FT-IR (KBr) 3448 (br), 3048 (m), 3020 (w), 2976 (w), 2929 (s), 2855 (w), 1623 (m), 1582 (m), 1513 (s), 1494 (m), 1452 (s), 1423 (s), 1370 (s), 1322 (m), 1263 (w), 1225 (m), 1205 (s), 1177 (m), 1144 (m), 1103 (m), 1048 (s), 977 (s), 904 (w), 852 (s), 817 (s), 781 (m), 751 (w), 728 (s), 699 (s), 645 (m), 625 (s), 585 (w), 559 (w), 534 (s), 508 (m), 482 (m), 419 (s)
UV–vis spectrum (MeOH, c = 7.4 × 10⁻⁵ M) peaks λ nm: 253, 457
UV–vis spectrum (MeCN, c = 8.3 × 10⁻⁵ M) peaks λ nm: 271, 293 465
ESI-HRMS m/z [C2-Cl]⁺ Calcd for [C₂₁H₂₃MnN₆O₃]⁺ 462.1207; Found 462.1207
Elemental analysis Calcd for C₂₁H₂₃ClMnN₆O₃·0.5CH₃OH: C, 50.25; H, 4.90; N, 16.35. Found: C, 50.67; H, 4.38; N, 16.05
SI, p. S5
Mn(TAAD)(bipy)Cl
Identifier C3
Mp above 210 °C
FT-IR (KBr) 3440 (br), 3107 (w), 3066 (w), 3025 (w), 2979 (w), 2936 (s), 2855 (w), 1633 (m), 1599 (s), 1568 (m), 1492 (s), 1471 (s), 1459 (s), 1442 (s), 1370 (s), 1314 (s), 1285 (w), 1266 (w), 1249 (w), 1210 (s), 1175 (s), 1159 (s), 1102 (w), 1046 (s), 1022 (s), 977 (s), 890 (w), 819 (s), 758 (s), 736 (s), 702 (s), 654 (s), 630 (s), 586 (w), 536 (s), 478 (w), 421 (w)
UV–vis spectrum (MeOH, c = 2.9 × 10⁻⁴ M) peaks λ nm: 292, 455
ESI-HRMS m/z [C3-Cl]⁺ Calcd for [C₁₉H₂₃MnN₆O₃]⁺ 438.1207; Found 438.1205
Elemental analysis Calcd for C₁₉H₂₃ClMnN₆O₃·1.5H₂O: C, 45.57; H, 5.23; N, 16.78. Found: C, 45.31; H, 4.76; N, 16.07
SI, p. S6
Mn2(TAAD)2(py)(OAc)2
Identifier C4
Decomposition above 193 °C without melting
FT-IR (KBr) 2930 (s,br), 1721 (m), 1581 (s), 1427 (s), 1375 (s), 1345 (m), 1327 (m), 1267 (m), 1209 (s), 1179 (m), 1052 (s), 979 (s), 884 (w), 817 (s), 760 (m), 701 (s), 654 (s), 627 (s), 534 (s), 498 (m), 418(m)
UV–vis spectrum (MeOH, c = 5 × 10⁻⁴ M) peaks λ nm: 290, 446
UV–vis spectrum (MeCN, c = 1.6 × 10⁻⁴ M) peaks λ nm: 293, 463
Elemental analysis Calcd for C₂₇H₄₁Mn₂N₉O₁₀·CH₃OH·Et₂O: C, 44.29; H, 6.39; N, 14.53. Found: C, 44.21; H, 5.88; N, 14.12
SI, p. S7
Mn2(TAAD)2(OMe)2(MeOH)2
Identifier C5
Mp 180-186 °C
FT-IR (KBr) 3381 (s,br), 1722 (w), 1602 (s), 1458 (s), 1436 (s), 1372 (s), 1330 (s), 1269 (m), 1212 (s), 1178 (s), 1048 (s), 980 (s), 864 (w), 830 (s), 779 (m), 760 (m), 702 (s), 658 (m), 629 (s), 599 (w), 535 (s), 460 (w), 420 (m)
UV–vis spectrum (MeOH, c = 5.0 × 10⁻⁴ M) peaks λ nm: 223, 293, 446, 578
Elemental analysis Calcd for C₂₀H₄₄Mn₂N₈O₁₂·4H₂O: C, 34.39; H, 6.35; N, 16.04. Found: C, 34.89; H, 6.40; N, 15.63
SI, p. S8
Na[Mn2(TAAD)2(OMe)3]
Identifier C6
Mp above 210 °C
FT-IR (KBr) 3445 (s,br), 2933 (s,br),1609 (s,br), 1457 (s), 1372 (s), 1327 (m), 1263 (w), 1208 (s), 1168 (m), 1082 (s), 1036 (s), 971 (m), 882 (w), 823 (s), 769 (w), 748 (w), 708 (s), 631 (s), 588 (w), 521 (s), 439 (s)
UV–vis spectrum (MeOH, c = 5.0 × 10⁻⁴ M) peaks λ nm: 245, 296, 461, 569
ESI-HRMS m/z [C6-Na-H₂O-MeOH]⁻ Calcd for [C₂₁H₃₉Mn₂N₈O₉]⁻ 657.1606; Found 657.1614
Elemental analysis Calcd for C₂₁H₃₉Mn₂N₈O₉Na·4H₂O·MeOH: C, 33.68; H, 6.55; N, 14.28. Found: C, 33.59; H, 5.41; N, 13.23
SI, p. S9
[Na(MeOH)2][Mn2(TAAD)2(OMe)2(OAc)]
Identifier C7
Mp above 210 °C
FT-IR (KBr) 3436 (s,br), 2934 (s,br), 1577 (s), 1424 (s), 1374 (s), 1333 (m), 1267 (w), 1210 (m), 1173 (m), 1130 (w), 1047 (s), 978 (m), 943 (w), 823 (s), 751 (w), 705 (s), 654 (m), 628 (m), 588 (w), 535 (s), 505 (s), 423 (m)
UV–vis spectrum (MeOH, c = 5.0 × 10⁻⁴ M) peaks λ nm: 238, 290, 450
ESI-HRMS m/z [C7-Na-2MeOH]⁻ Calcd for [C₂₂H₃₉Mn₂N₈O₁₀]⁻ 685.1556; Found 685.1537. [Mn(TAAD)]⁺ Calcd for [C₉H₁₅MnN₄O₃]⁺ 282.0519; Found 282.0534
Elemental analysis Calcd for C₂₂H₃₉Mn₂N₈O₁₀Na·2H₂O·2MeOH: C, 35.65; H, 6.36; N, 13.86. Found: C, 36.18; H, 5.73; N, 12.51
SI, p. S10
Mn2(TAAD)2(μ-N3)2(MeOH)2
Identifier C8
Mp above 210 °C
FT-IR (KBr) 3392 (m,br), 2982 (w), 2938 (m), 2138 (s), 2080 (s), 1635 (m,br), 1554 (m), 1457 (m), 1433 (m), 1374 (m), 1345 (m), 1293 (w), 1267 (w), 1210 (m), 1178 (m), 1049 (s), 979 (m), 880 (w), 825 (s), 752 (w), 701 (m), 665 (m), 630 (m), 593 (w), 535 (s), 507 (m), 420 (m)
UV–vis spectrum (MeOH, c = 5.0 × 10⁻⁴ M) peaks λ nm: 205, 293, 448, 585
SI, p. S11
[Mn(TAAD)(tacn)]Cl obtained by transformation of C4
Identifier C1
FT-IR (KBr) 3445 (br), 3361 (br), 3268 (s), 3152 (br), 2946 (br), 1634 (s), 1457 (s), 1434 (s), 1376 (s), 1356 (m), 1323 (m), 1269 (m), 1217 (s), 1180 (m), 1150 (m), 1099 (s), 1072 (s), 1029 (s), 994 (m), 972 (s), 949 (s), 872 (m), 826 (s), 793 (m), 749 (m), 704 (s), 627 (s), 585 (s), 541 (s), 511 (s), 416 (s)
Selected IR frequencies 1099 (s), 1072 (s), 1029 (s)
Selected IR frequency, C4 654 (s)
UV–vis spectrum (MeOH, c = 5.0 × 10⁻⁴ M) peaks λ nm: 293, 460, 546
ESI-HRMS m/z [C1-Cl]⁺ Calcd for [C₁₅H₃₀MnN₇O₃]⁺ 411.1785; Found 411.1786
Elemental analysis Calcd for C₁₅H₃₀ClMnN₇O₃·4H₂O: C, 34.72; H, 7.38; N, 18.90. Found: C, 35.17; H, 7.88; N, 18.30
SI, p. S12
Na[Mn2(TAAD)2(OMe)3] obtained by transformation of C4
Identifier C6
FT-IR (KBr) 3426 (s,br), 2934 (s,br), 1631 (s), 1561 (s), 1456 (s), 1429 (s) 1371 (s), 1346 (m), 1327 (m), 1265 (w), 1210 (s), 1166 (m), 1040 (s,br), 975 (m), 881 (w), 825 (s), 752 (w), 708 (s), 669 (w), 632 (m), 589 (w), 537 (s), 504 (s), 435 (s), 421 (s)
UV–vis spectrum (MeOH, c = 5.0 × 10⁻⁴ M) peaks λ nm: 225, 294, 460, 580
ESI-HRMS m/z [C6-Na-H₂O-MeOH]⁻ Calcd for [C₂₁H₃₉Mn₂N₈O₉]⁻ 657.1601; Found 657.1607. [Mn₂(TAAD)₂(OMe)(OH)(OAc)]⁻ Calcd for [C₂₁H₃₇Mn₂N₈O₁₀]⁻ 671.1399; Found 671.1409. [Mn(TAAD)]⁺ Calcd for [C₉H₁₅MnN₄O₃]⁺ 282.0519; Found 282.0534
Elemental analysis Calcd for C₂₁H₃₉Mn₂N₈O₉Na·2H₂O·3MeOH: C, 35.47; H, 6.82; N, 13.79. Found: C, 35.93; H, 5.68; N, 12.76
SI, p. S13
[Na(MeOH)2][Mn2(TAAD)2(OMe)2(OAc)] obtained by transformation of C6
Identifier C7
FT-IR (KBr) 3404 (br), 2933 (s,br), 1733 (m), 1576 (s), 1420 (s), 1374 (s), 1341 (s), 1300 (w), 1265 (w), 1233 (m), 1210 (m), 1168 (m), 1130 (w), 1041 (s), 979 (s), 942 (s), 821 (s), 704 (s), 658 (s), 627 (m), 586 (w), 535 (s), 508 (m), 443 (w), 421 (m)
UV–vis spectrum (MeOH, c = 5.0 × 10⁻⁴ M) peaks λ nm: 205, 279, 451, 578
ESI-HRMS m/z [C7-Na-2MeOH]⁻ Calcd for [C₂₂H₃₉Mn₂N₈O₁₀]⁻ 685.1556; Found 685.1520. [Mn₂(TAAD)₂(OMe)(OH)(OAc)]⁻ Calcd for [C₂₁H₃₇Mn₂N₈O₁₀]⁻ 671.1399; Found 671.1370
Elemental analysis Calcd for C₂₂H₃₉Mn₂N₈O₁₀Na·2MeOH: C, 37.31; H, 6.13 N, 14.40. Found: C, 39.07; H, 5.48; N, 14.21
SI, p. S14
1,4,6,10-tetraazaadamantane-based tris-hydroxylamine hydrochloride
Identifier TAAD-H3·HCl
Method Single-crystal X-ray diffraction
Formula C₉H₁₉ClN₄O₃
Formula weight 266.73
T, K 100
Crystal system Monoclinic
Space group P21/n
Z 4
a, Å 8.6716(4)
b, Å 11.6642(7)
c, Å 11.8025(6)
α, ° 90
β, ° 91.032(4)
γ, ° 90
V, ų 1193.60(11)
Dcalc (g cm⁻¹) 1.484
Linear absorption, μ (cm⁻¹) 29.04
F(000) 568
2θmax, ° 150
Reflections measured 4835
Independent reflections 4835
Observed reflections [I > 2σ(I)] 4467
Parameters 170
R1 0.0707
wR2 0.2298
GOF 1.123
Δρmax/Δρmin (e Å⁻³) 0.505/-0.730
Main, p. 4; SI, p. S53
[Mn(TAAD)(tacn)]Cl·2H2O
Identifier C1
Method Single-crystal X-ray diffraction
Formula C₁₅H₃₄ClMnN₇O₅
Formula weight 482.88
T, K 100
Crystal system Orthorhombic
Space group Ibam
Z 16
a, Å 14.20742(15)
b, Å 21.1492(2)
c, Å 30.6515(3)
α, ° 90
β, ° 90
γ, ° 90
V, ų 9210.03(16)
Dcalc (g cm⁻¹) 1.393
Linear absorption, μ (cm⁻¹) 7.28
F(000) 4080
2θmax, ° 56
Reflections measured 77651
Independent reflections 5671
Observed reflections [I > 2σ(I)] 5330
Parameters 261
R1 0.0360
wR2 0.0968
GOF 1.118
Δρmax/Δρmin (e Å⁻³) 0.842/-0.329
Main, pp. 3–4, 8; SI, p. S53
Mn(TAAD)(phen)Cl·MeOH
Identifier C2
Method Single-crystal X-ray diffraction
Formula C₂₂H₂₇ClMnN₆O₄
Formula weight 529.88
T, K 100
Crystal system Monoclinic
Space group P21/n
Z 8
a, Å 13.47950(10)
b, Å 23.2409(3)
c, Å 15.5143(2)
α, ° 90
β, ° 108.2610(10)
γ, ° 90
V, ų 4615.49(9)
Dcalc (g cm⁻¹) 1.525
Linear absorption, μ (cm⁻¹) 60.82
F(000) 2200
2θmax, ° 150
Reflections measured 38260
Independent reflections 9372
Observed reflections [I > 2σ(I)] 7911
Parameters 625
R1 0.0554
wR2 0.1497
GOF 1.033
Δρmax/Δρmin (e Å⁻³) 1.277/-0.673
Main, pp. 3–4; SI, p. S53
Mn(TAAD)(bipy)Cl
Identifier C3
Method Single-crystal X-ray diffraction
Formula C₁₉H₂₃ClMnN₆O₃
Formula weight 473.82
T, K 100
Crystal system Monoclinic
Space group P21/n
Z 4
a, Å 13.6436(2)
b, Å 11.4362(2)
c, Å 13.7374(2)
α, ° 90
β, ° 115.696(2)
γ, ° 90
V, ų 1931.49(6)
Dcalc (g cm⁻¹) 1.629
Linear absorption, μ (cm⁻¹) 71.47
F(000) 980
2θmax, ° 150
Reflections measured 25776
Independent reflections 3958
Observed reflections [I > 2σ(I)] 3845
Parameters 275
R1 0.0556
wR2 0.1428
GOF 1.174
Δρmax/Δρmin (e Å⁻³) 0.667/-0.488
Main, pp. 3–4; SI, p. S53
Mn2(TAAD)2(py)(OAc)2
Identifier C4
Method Single-crystal X-ray diffraction
Formula C₂₇H₄₁Mn₂N₉O₁₀
Formula weight 761.57
T, K 100
Crystal system Monoclinic
Space group P21/c
Z 4
a, Å 11.7126(2)
b, Å 16.8343(2)
c, Å 16.4928(2)
α, ° 90
β, ° 99.7150(10)
γ, ° 90
V, ų 3205.31(8)
Dcalc (g cm⁻¹) 1.578
Linear absorption, μ (cm⁻¹) 70.2
F(000) 1584
2θmax, ° 136
Reflections measured 45317
Independent reflections 5791
Observed reflections [I > 2σ(I)] 5331
Parameters 441
R1 0.0244
wR2 0.0628
GOF 1.049
Δρmax/Δρmin (e Å⁻³) 0.263/-0.256
Main, p. 6; SI, p. S54
Na[Mn2(TAAD)2(OMe)3]
Identifier C6
Method Single-crystal X-ray diffraction
Formula C₂₂H₄₅Mn₂N₈NaO₁₁
Formula weight 730.53
T, K 100
Crystal system Monoclinic
Space group P21/c
Z 4
a, Å 8.64150(10)
b, Å 18.25230(10)
c, Å 19.61690(10)
α, ° 90
β, ° 98.3890(10)
γ, ° 90
V, ų 3061.01(4)
Dcalc (g cm⁻¹) 1.585
Linear absorption, μ (cm⁻¹) 74.58
F(000) 1528
2θmax, ° 150
Reflections measured 40321
Independent reflections 6295
Observed reflections [I > 2σ(I)] 6032
Parameters 408
R1 0.0399
wR2 0.1022
GOF 1.074
Δρmax/Δρmin (e Å⁻³) 0.887/-0.696
Main, p. 6; SI, p. S54
[Na(MeOH)2][Mn2(TAAD)2(OMe)2(OAc)]·MeOH
Identifier C7
Method Single-crystal X-ray diffraction
Formula C₂₄H₅₁Mn₂N₈NaO₁₃
Formula weight 804.60
T, K 100
Crystal system Monoclinic
Space group P21
Z 2
a, Å 8.99420(10)
b, Å 18.4963(2)
c, Å 10.95550(10)
α, ° 90
β, ° 101.4620(10)
γ, ° 90
V, ų 1786.20(3)
Dcalc (g cm⁻¹) 1.496
Linear absorption, μ (cm⁻¹) 64.89
F(000) 844
2θmax, ° 150
Reflections measured 21754
Independent reflections 6856
Observed reflections [I > 2σ(I)] 6658
Parameters 455
R1 0.0312
wR2 0.0838
GOF 1.045
Δρmax/Δρmin (e Å⁻³) 0.618/-0.288
Main, p. 7; SI, p. S54
[Mn(TAAD)(tacn)]Cl in CD₃OD
Identifier C1
Magnetic susceptibility (300 MHz, CD₃OD) χM_dia = -2,83*10⁻⁴; conc (M) = 2,64*10⁻²; ppm_dia = 0,00; ppm_para = 0,80; Δ (ppm) = 0,80; χM_para (cm³ mol⁻¹) = 7,23*10⁻³; χM = 6,95*10⁻³; μeff = 4,15; n = 3,27; μB = 3,87; n = 3,00; err = 6,73
Main, p. 7; SI, p. S63
Mn(TAAD)(phen)Cl in CD₃OD
Identifier C2
Magnetic susceptibility (300 MHz, CD₃OD) χM_dia = -2,97*10⁻⁴; conc (M) = 2,25*10⁻²; ppm_dia = 0,00; ppm_para = 0,62; Δ (ppm) = 0,62; χM_para (cm³ mol⁻¹) = 6,58*10⁻³; χM = 6,28*10⁻³; μeff = 3,96; n = 3,08; μB = 3,87; n = 3,00; err = 2,21
Main, p. 7; SI, p. S63
Mn(TAAD)(bipy)Cl in CD₃OD
Identifier C3
Magnetic susceptibility (300 MHz, CD₃OD) χM_dia = -2,60*10⁻⁴; conc (M) = 2,57*10⁻²; ppm_dia = 0,00; ppm_para = 0,77; Δ (ppm) = 0,77; χM_para (cm³ mol⁻¹) = 7,14*10⁻³; χM = 6,88*10⁻³; μeff = 4,14; n = 3,26; μB = 3,87; n = 3,00; err = 6,44
Main, p. 7; SI, p. S63
Mn2(TAAD)2(py)(OAc)2 in CD₃OD
Identifier C4
Magnetic susceptibility (300 MHz, CD₃OD) χM_dia = -3,96*10⁻⁴; conc (M) = 1,47*10⁻²; ppm_dia = 0,00; ppm_para = 0,65; Δ (ppm) = 0,65; χM_para (cm³ mol⁻¹) = 1,06*10⁻²; χM = 1,02*10⁻²; μeff = 5,03; n = 4,13; μB = 4,90; n = 4,00; err = 2,65
Main, p. 7; SI, p. S63
Na[Mn2(TAAD)2(OMe)3] in CD₃OD
Identifier C6
Magnetic susceptibility (300 MHz, CD₃OD) χM_dia = -2,88*10⁻⁴; conc (M) = 2,83*10⁻²; ppm_dia = 0,00; ppm_para = 1,13; Δ (ppm) = 1,13; χM_para (cm³ mol⁻¹) = 9,52*10⁻³; χM = 9,23*10⁻³; μeff = 4,76; n = 3,87; μB = 4,90; n = 4,00; err = 2,83
Main, p. 7; SI, p. S63
1-phenylcyclohexene
Identifier S1a
Rf (petroleum ether) 0.3
¹H NMR (300 MHz, CDCl₃, δ, ppm) 7.45 – 7.42 (m, 2H, HPh), 7.38 – 7.33 (m, 2H, HPh), 7.28 – 7.23 (m, 1H, HPh), 6.17 (tt, J = 3.9, 1.7 Hz, 1H, =CH), 2.50 – 2.44 (m, 2H, CH2), 2.31 – 2.23 (m, 2H, CH2), 1.88 – 1.80 (m, 2H, CH2), 1.75 – 1.68 (m, 2H, CH2)
SI, p. S114
1-(4-methoxyphenyl)-cyclohexene
Identifier S1b
Rf (petroleum ether) 0.2
Mp 36-38 °C
¹H NMR (300 MHz, CDCl₃, δ, ppm) 7.33 (d, J = 8.7 Hz, 2H, HAr), 6.86 (d, J = 8.7 Hz, 2H, HAr), 6.10 – 6.00 (m, 1H, =CH), 3.81 (s, 3H, OCH3), 2.44 – 2.34 (m, 2H, CH2), 2.25 – 2.16 (m, 2H, CH2), 1.83 – 1.75 (m, 2H, CH2), 1.70 – 1.62 (m, 2H, CH2)
SI, p. S115
1-(4-fluorophenyl)-cyclohexene
Identifier S1c
Rf (petroleum ether) 0.3
Mp 23-26 °C
¹H NMR (300 MHz, CDCl₃, δ, ppm) 7.39 – 7.29 (m, 2H, HAr), 6.99 (t, J = 8.6 Hz, 2H, HAr), 6.07 – 6.04 (m, 1H, =CH), 2.43 – 2.33 (m, 2H, CH2), 2.25 – 2.16 (m, 2H, CH2), 1.83 – 1.75 (m, 2H, CH2), 1.70 – 1.62 (m, 2H, CH2)
SI, p. S115
1-(3-methylphenyl)-cyclohexene
Identifier S1d
Rf (petroleum ether) 0.3
¹H NMR (300 MHz, CDCl₃, δ, ppm) 7.24 – 7.18 (m, 3H, HAr), 7.11 – 7.03 (m, 1H, HAr), 6.13 (tt, J = 3.8, 1.7 Hz, 1H, =CH), 2.48 – 2.41 (m, 2H, CH2), 2.38 (s, 3H, CH3), 2.29 – 2.197 (m, 2H, CH2), 1.85 – 1.77 (m, 2H, CH2), 1.73 – 1.65 (m, 2H, CH2)
SI, p. S115
6-oxo-6-phenylhexanenitrile
Identifier S2a
Rf (petroleum ether-EtOAc = 3:1) 0.3
Mp 62-64 °C
¹H NMR (300 MHz, CDCl₃, δ, ppm) 7.95 (d, J = 7.3 Hz, 2H, HPh), 7.58 (t, J = 7.3 Hz, 1H, HPh), 7.47 (t, J = 7.3 Hz, 2H, HPh), 3.07 – 3.02 (m, 2H, CH2C=O), 2.41 (t, J = 7.0 Hz, 2H, CH2CN), 1.96 – 1.87 (m, 2H, CH2), 1.81 – 1.72 (m, 2H, CH2)
¹³C {¹H} NMR (75 MHz, DEPT135, CDCl₃, δ, ppm) 199.2 (1C, C=O), 136.8 (1C, CPh), 133.4 (1C, CHPh), 128.8 (2C, CHPh), 128.1 (2C, CHPh), 119.7 (1C, CN), 37.5 (1C, CH2), 25.2 (1C, CH2), 23.2 (1C, CH2), 17.4 (1C, CH2)
SI, p. S121
(1,2-diazidocyclohexyl)benzene
Identifier S3a
Rf (petroleum ether) 0.5
¹H NMR (300 MHz, HSQC, CDCl₃, δ, ppm) 7.51 – 7.34 (m, 5H, HPh), 3.79 – 3.77 (m, 1H, CHN3), 2.42 – 2.27 (m, 1H, CH2), 2.16 – 1.98 (m, 2H, CH2), 1.88 – 1.69 (m, 3H, CH2), 1.64 – 1.51 (m, 2H, CH2)
¹³C {¹H} NMR (75 MHz, DEPT135, HSQC, CDCl₃, δ, ppm) 141.1 (1C, CPh), 128.91 (2C, CHPh), 128.54 (1C, CHPh), 126.7 (2C, CHPh), 67.9 (1C, CN3), 65.4 (1C, CHN3), 27.7 (1C, CH2), 26.7 (1C, CH2), 21.3 (1C, CH2), 19.4 (1C, CH2)
ESI-HRMS m/z [S3a+Na]⁺ Calcd for [C₁₂H₁₄N₆Na]⁺ 265.1172; Found 265.1172
SI, p. S121
6-(4-methoxyphenyl)-6-oxohexanenitrile
Identifier S2b
Rf (petroleum ether-EtOAc = 3:1) 0.3
Mp 58-59 °C
¹H NMR (300 MHz, CDCl₃, δ, ppm) 7.93 (d, J = 8.9 Hz, 2H, HAr), 6.94 (d, J = 8.9 Hz, 2H, HAr), 3.87 (s, 3H, OCH3), 2.99 (t, J = 6.9 Hz, 2H, CH2C=O), 2.40 (t, J = 7.0 Hz, 2H, CH2CN), 1.95 – 1.85 (m, 2H, CH2), 1.80 – 1.71 (m, 2H, CH2)
¹³C {¹H} NMR (75 MHz, DEPT135, CDCl₃, δ, ppm) 197.8 (1C, C=O), 163.7 (1C, CAr), 130.4 (1C, CAr), 129.9 (2C, CHAr), 119.7 (1C, CN), 113.9 (2C, CHAr), 55.6 (1C, OCH3), 37.1 (1C, CH2), 25.2 (1C, CH2), 23.4 (1C, CH2), 17.3 (1C, CH2)
ESI-HRMS m/z [S2b+Na]⁺ Calcd for [C₁₃H₁₅NO₂Na]⁺ 240.0995; Found 240.1004
SI, p. S122
6-(4-fluorophenyl)-6-oxohexanenitrile
Identifier S2c
Rf (petroleum ether-EtOAc = 3:1) 0.3
¹H NMR (300 MHz, CDCl₃, δ, ppm) 7.97 (dd, J = 8.9, 5.4 Hz, 2H, HAr), 7.13 (t, J = 8.9 Hz, 2H, HAr), 3.01 (t, J = 6.9 Hz, 2H, CH2C=O), 2.40 (t, J = 7.0 Hz, 2H, CH2CN), 1.95 – 1.84 (m, 2H, CH2), 1.80 – 1.71 (m, 2H, CH2)
¹³C {¹H} NMR (75 MHz, DEPT135, CDCl₃, δ, ppm) 197.5 (1C, C=O), 165.9 (d, J = 254.9 Hz, 1C, CAr), 133.2 (d, J = 3.1 Hz, 1C, CAr), 130.7 (d, J = 9.3 Hz, 2C, CHAr), 119.6 (1C, CN), 115.9 (d, J = 21.9 Hz, 2C, CHAr), 37.4 (1C, CH2), 25.1 (1C, CH2), 23.2 (1C, CH2), 17.3 (1C, CH2)
¹⁹F NMR (282 MHz, CDCl₃, δ, ppm) -105.03
ESI-HRMS m/z [S2c+Na]⁺ Calcd for [C₁₂H₁₂FNONa]⁺ 228.0795; Found 228.0800
SI, p. S122
6-(3-methylphenyl)-6-oxohexanenitrile
Identifier S2d
Rf (petroleum ether-EtOAc = 3:1) 0.4
¹H NMR (300 MHz, CDCl₃, δ, ppm) 7.75 – 7.73 (m, 2H, HAr), 7.42 – 7.32 (m, 2H, HAr), 3.02 (t, J = 6.8 Hz, 2H, CH2C=O), 2.41 (s, 3H, CH3), 2.40 (t, J = 7.0 Hz, 2H, CH2CN), 1.95 – 1.85 (m, 2H, CH2), 1.80 – 1.70 (m, 2H, CH2)
¹³C {¹H} NMR (75 MHz, DEPT135, CDCl₃, δ, ppm) 199.4 (1C, C=O), 138.6 (1C, CAr), 136.9 (1C, CAr), 134.1 (1C, CHAr), 128.65 (1C, CHAr), 128.61 (1C, CHAr), 125.3 (1C, CHAr), 119.6 (1C, CN), 37.5 (1C, CH2C=O), 25.2 (1C, CH2), 23.3 (1C, CH2), 21.5 (1C, CH3), 17.3 (1C, CH2CN)
ESI-HRMS m/z [S2d+Na]⁺ Calcd for [C₁₃H₁₅NONa]⁺ 224.1046; Found 224.1053
SI, p. S123
[Mn(TAAD)(tacn)]Cl in DMSO
Identifier C1
Cyclic voltammetry (5 mM complex, 100 mM TBAPF6 in DMSO, Pt disk working and counter electrodes, Pt wire ref. electrode, vs. Fc/Fc+, 100 mV/s) first broad peak ca. −1.5 V; E1/2 = −1.89 V
Main, pp. 10–11
Mn(TAAD)(phen)Cl in DMSO
Identifier C2
Cyclic voltammetry (5 mM complex, 100 mM TBAPF6 in DMSO, Pt disk working and counter electrodes, Pt wire ref. electrode, vs. Fc/Fc+, 100 mV/s) first broad peak ca. −1.5 V; Ered2 = −1.71 V
Main, pp. 10–11
Mn(TAAD)(bipy)Cl in DMSO
Identifier C3
Cyclic voltammetry (5 mM complex, 100 mM TBAPF6 in DMSO, Pt disk working and counter electrodes, Pt wire ref. electrode, vs. Fc/Fc+, 100 mV/s) first broad peak −1.04 V; Ered2 = −1.5 V
Main, pp. 10–11
Mn2(TAAD)2(py)(OAc)2 in DMSO
Identifier C4
Cyclic voltammetry (5 mM complex, 100 mM TBAPF6 in DMSO, Pt disk working and counter electrodes, Pt wire ref. electrode, vs. Fc/Fc+, 100 mV/s) Epc1 = −1.11 V; Epc2 = −1.50 V; Epc3 = −1.87 V
Main, pp. 11–12
Mn(IV)–TAAD complexes
Identifiers C1–C8
UV–Vis a strong absorption band at ca. 450 nm and a broader lower energy band with a tail around 500 nm; in UV region, a characteristic band at ca. 290 nm
Emission No emission was observed in solution or PMMA films even at 77 K
Main, p. 9
Mn(IV)–TAAD complexes in acetonitrile at room temperature
Identifiers C1, C2, and C4
UV–Vis stability monitoring The red-colored solution of pyridine complex C4 in acetonitrile becomes almost completely decolorized at room temperature within a week. In comparison, only partial decomposition of mononuclear complexes C1 and C2 was detected by UV-Vis within this time period
Main, p. 7
Mn(TAAD)(phen)Cl under 420 nm irradiation
Identifier C2
Photodegradation (420 nm) ca. 40 % decrease of absorbance at 466 nm after 5 h