Магнитно-Резонансные Параметры Нитроксильных Радикалов

Do, ut des

Высокое спектральное разрешение 2-мм ЭПР спектроскопии позволяет раздельно определить все главные значения g- и A-тензоров.
Контролируя измение формы всех спектральных компонент, можно установить влияние различных факторов на распределение неспаренного электрона в молекуле.
Высокое спектральное разрешение предоставляет также возможность раздельно определить анизотропию и частоту вращения нитроксильного радикала и его ближайшего окружения. Это может быть осуществлено при помощи регистрации компонент поглощения (область "быстрого" вращения) или дисперсии (область "медленного" и "сверхмедленного" вращения).

Радикал

Матрица

g_xx

g_yy

g_zz

A_xx,
мТл

A_yy,
мТл

A_zz,
мТл

a_iso,
мТл

Ациклические радикалы

C₆H₅CH₃

2.00944

2.00622

2.00228

0.59

3.42

C₁₀H₁₈

2.00886

2.00615

2.00220

3.58

C₆H₅CH₃

2.00901

2.00538

2.00236

2.57

1.01

C₁₀H₁₈

2.00783

2.00498

2.00225

2.77

C₆H₅C(CH₃)₃

2.00947

2.00541

2.00217

2.50

C₆H₅CH₃

2.00907

2.00522

2.00226

2.47

C₁₀H₁₈

2.00947

2.00822

2.00518

2.00224

2.49

CH₃OH

2.00913

2.00812

2.00521

2.00213

2.61

C₉H₁₉CHOH

2.00934

2.00846

2.00520

2.00214

2.46

Пиперидиновая серия

C₆H₅C(CH₃)₃

2.00975

2.00636

2.00218

3.37

Caoutchouc

2.00988

2.00611

2.00224

3.35

NM

2.00980

2.00611

2.00222

3.41

C₆H₅CH₃

2.00980

2.00622

2.00220

0.60

0.73

3.42

1.55

CH₃OH

2.00909

2.00621

2.00222

0.72

3.64

C₁₀H₁₈

2.00920

2.00625

2.00226

3.52

C₇H₁₆

2.00915

2.00619

2.00220

0.48

0.54

3.32

1.43

C₆H₅CH₃

2.00918

2.00620

2.00220

3.33

C₁₀H₁₈

2.00883

2.00620

2.00225

3.55

CH₃OH

2.00870

2.00618

2.00217

3.58

C₆H₅CH₃

2.00978

2.00625

2.00217

0.63

0.69

3.40

1.57

C₆H₅CH₃

2.00966

2.00627

2.00221

3.40

C₆H₅CH₃

2.00979

2.00625

2.00220

3.49

C₆H₅CH₃

2.00971

2.00622

2.00221

3.43

C₆H₅CH₃

2.00974

2.00623

2.00222

3.41

CH₃OH

2.00919

2.00611

2.00214

3.57

C₆H₅C(CH₃)₃

2.00981

2.00601

2.00162

0.95

0.71

3.51

1.72

C₆H₅CH₃

2.00988

2.00628

2.00232

0.64

0.72

3.48

1.61

C₆H₅CH₃

2.00988

2.00625

2.00222

0.66

0.71

3.40

1.55

C₆H₅CH₃

2.00986

2.00626

2.00222

0.62

0.70

3.43

1.58

HM

2.00978

2.00624

2.00221

0.62

0.69

3.45

1.54

C₅H₁₁OH

2.00922

2.00607

2.00218

0.68

3.61

C₁₀H₁₈

2.00917

2.00608

2.00216

0.77

3.58

C₂H₅OH

2.00903

2.00616

2.00218

3.63

CH₃OH

2.00899

2.00610

2.00218

0.73

3.70

H₂O

2.00878

2.00604

2.00215

3.74

C₆H₅CH₃

2.00984

2.00629

2.00226

3.43

HM

2.00967

2.00627

2.00225

0.66

3.39

CH₃OH

2.00901

2.00620

2.00222

3.69

1.61

C₆H₅CH₃

2.00986

2.00626

2.00230

0.65

0.74

3.35

1.53

HM

2.00974

2.00641

2.00228

0.66

3.38

C₆H₅CH₃

2.00990

2.00627

2.00220

0.64

0.71

3.38

1.52

HM

2.00967

2.00621

2.00228

3.44

CH₃OH

2.00918

2.00623

2.00221

3.65

1.62

C₆H₅CH₃

2.00985

2.00623

2.00223

CH₃OH

2.00901

2.00610

2.00216

C₆H₅CH₃

2.00991

2.00619

2.00218

3.44

1.52

HM

2.00988

2.00635

2.00233

3.40

CH₃OH

2.00937

2.00613

2.00219

3.53

C₆H₅CH₃

2.00986

2.00624

2.00216

0.62

0.68

3.34

1.55

C₆H₅CH₃

2.00991

2.00622

2.00235

0.64

0.69

3.38

1.49

HM

2.00984

2.00631

2.00227

0.66

3.36

CH₃OH

2.00935

2.00880

2.00620

2.00232

3.49

C₆H₅CH₃

2.01005

2.00640

2.00223

0.43

0.66

3.38

1.49

HM

2.00970

2.00624

2.00222

3.36

CH₃OH

2.00942

2.00882

2.00634

2.00232

3.51

C₆H₅CH₃

2.00952

2.00632

2.00192

3.38

1.50

C₆H₅CH₃

2.00915

2.00621

2.00217

3.35

1.44

HM

2.00977

2.00634

2.00232

3.33

CH₃OH

2.00874

2.00610

2.00216

3.44

3-Пиперидиновая серия

C₆H₅CH₃

2.00967

2.00619

2.00228

3.33

C₁₀H₁₈

2.00933

2.00624

2.00225

3.41

C₆H₅CH₃

2.00969

2.00624

2.00218

3.36

C₉H₁₉CHOH

2.00896

2.00605

2.00210

3.48

CH₃OH

2.00884

2.00598

2.00211

3.59

C₆H₅CH₃

2.00970

2.00621

2.00225

3.37

NM

2.00957

2.00613

2.00223

3.36

C₆H₅C(CH₃)₃

2.00979

2.00622

2.00206

3.41

C₉H₁₉CHOH

2.00936

2.00617

2.00228

3.41

C₃H₇OH

2.00924

2.00619

2.00218

3.49

NH₂CH₂CO₂H

2.00896

2.00606

2.00218

3.51

C₆H₅CH₃

2.00971

2.00623

2.00218

3.33

Vaseline

2.00969

2.00611

2.00228

3.21

Caoutchouc

2.00986

2.00611

2.00226

3.34

NM

2.00961

2.00624

2.00228

3.35

CH₃OH

2.00915

2.00604

2.00205

3.60

C₆H₅CH₃

2.00971

2.00618

2.00211

3.36

NM

2.00950

2.00615

2.00220

3.35

C₉H₁₉CHOH

2.00876

2.00585

2.00209

3.43

C₆H₅C(CH₃)₃

2.00998

2.00627

2.00230

3.31

C₆H₅CH₃

2.00953

2.00577

2.00176

3.40

C₅H₁₁OH

2.01010

2.00935

2.00602

2.00197

3.50

C₂H₅OH

2.00910

2.00573

2.00210

3.58

3C₂H₅OH/H₂O

2.00902

2.00543

2.00212

3.60

C₂H₅OH/H₂O

2.00890

2.00602

2.00214

3.65

C₂H₅OH/2H₂O

2.00883

2.00608

2.00201

3.70

CH₃OH

2.00860

2.00550

2.00178

3.73

H₂O

2.00834

2.00571

2.00167

3.77

C₆H₅CH₃

2.00990

2.00614

2.00225

0.66

0.71

3.43

1.55

(CH₃)₂CHOH

2.00990

2.00621

2.00207

3.51

C₅H₁₁OH

2.00990

2.00940

2.00602

2.00197

3.56

C₂H₅OH

2.00942

2.00897

2.00592

2.00188

3.60

CH₃OH

2.00881

2.00558

2.00197

3.72

H₂O

2.00863

2.00582

2.00187

3.77

C₆H₅CH₃

2.00954

2.00606

2.00214

3.28

H₂O

2.00860

2.00610

2.00218

3.81

C₆H₅CH₃

2.00963

2.00617

2.00222

3.40

HM

2.00962

2.00624

2.00231

3.39

CH₃OH

2.00890

2.00612

2.00222

3.65

1.56

C₆H₅CH₃

2.00965

2.00630

2.00227

3.39

1.52

CH₃OH

2.00889

2.00609

2.00216

3.62

1.58

HM

2.00985

2.00618

2.00226

0.68

3.45

CH₃OH

2.00916

2.00619

2.00226

3.64

1.63

C₆H₅CH₃

2.00975

2.00632

2.00228

3.39

HM

2.00954

2.00620

2.00219

0.68

3.41

Пирролидиновая серия

C₆H₅CH₃

2.00893

2.00607

2.00222

0.43

0.48

3.30

1.40

CH₃OH

2.00821

2.00603

2.00220

3.59

C₆H₅CH₃

2.00915

2.00613

2.00220

0.41

0.47

3.33

1.37

C₆H₅CH₃

2.00907

2.00618

2.00217

3.30

Пирролиновая серия

HM

2.00898

2.00592

2.00219

3.41

HM

2.00901

2.00601

2.00211

3.29

1.46

C₂H₅OH

2.00868

2.00588

2.00214

3.41

CH₃OH

2.00840

2.00610

2.00219

3.66

C₆H₅CH₃

2.00933

2.00623

2.00205

3.34

C₅H₁₁OH

2.00930

2.00615

2.00206

3.38

(CH₃)₂CHOH

2.00925

2.00614

2.00208

3.41

C₂H₅OH

2.00861

2.00612

2.00212

3.49

CH₃OH

2.00835

2.00628

2.00214

3.60

H₂O

2.00828

2.00621

2.00215

3.65

C₆H₅CH₃

2.00927

2.00616

2.00219

3.26

C₆H₅CH₃

2.00859

2.00602

2.00211

0.49

0.53

3.40

1.47

C₂H₅OH

2.00849

2.00610

2.00215

3.61

C₆H₅CH₃

2.00902

2.00618

2.00217

3.38

C₈H₁₈

2.00872

2.00623

2.00214

3.43

C₂H₅OH

2.00865

2.00622

2.00221

3.52

CH₃OH

2.00857

2.00617

2.00209

3.69

Имидазолиновая серия

C₆H₅CH₃

2.00932

2.00604

2.00222

2.32

1.26

C₆H₅CH₃

2.00910

2.00613

2.00224

3.35

CH₃OH

2.00922

2.00862

2.00602

2.00221

3.45

C₆H₅CH₃

2.00913

2.00610

2.00228

3.27

CH₃OH

2.00923

2.00865

2.00607

2.00223

3.42

C₆H₅CH₃

2.00908

2.00610

2.00223

3.31

1.42

CH₃OH

2.00919

2.00862

2.00604

2.00221

3.41

1.48

CH₃OH

2.00958

2.00608

2.00218

3.25

C₆H₅CH₃

2.00881

2.00590

2.00206

3.36

CH₃OH

2.00807

2.00598

2.00210

3.49

CH₃OH

2.00858

2.00606

2.00214

3.48

C₆H₅CH₃

2.00909

2.00610

2.00221

0.46

0.51

3.24

1.40

C₆H₅CH₃

2.00916

2.00614

2.00223

3.32

CH₃OH

2.00926

2.00860

2.00611

2.00222

3.42

CH₃OH

2.00923

2.00864

2.00607

2.00224

3.40

1.44

HM

2.00890

2.00591

2.00216

3.32

C₆H₅C(CH₃)₃

2.00928

2.00614

2.00206

3.25

C₆H₅CH₃

2.00893

2.00592

2.00210

0.47

3.33

CH₃OH

2.00932

2.00879

2.00610

2.00223

3.42

C₆H₅CH₃

2.00902

2.00601

2.00223

3.26

CH₃OH

2.00871

2.00604

2.00223

3.38

CH₃OH

2.00958

2.00608

2.00218

3.25

CH₃OH

2.00921

2.00863

2.00609

2.00214

3.42

HM

2.00882

2.00594

2.00208

3.35

C₂H₅OH

2.01044

2.00984

2.00696

2.00302

3.39

C₈H₁₈

2.00951

2.00611

2.00215

3.28

C₃H₇OH

2.00955

2.00894

2.00619

2.00217

3.29

C₂H₅OH

2.00901

2.00617

2.00219

3.42

CH₃OH

2.00882

2.00626

2.00228

3.61

3-Имидазолин-3-оксид-1-оксиловая серия

C₆H₅CH₃

2.01100

2.00650

2.00210

1.86

C₆H₅CH₃

2.00927

2.00618

2.00224

0.47

0.55

3.22

1.44

Vaseline

2.00950

2.00614

2.00232

0.42

0.68

3.14

1.41

HM

2.00930

2.00616

2.00232

0.42

0.58

3.25

1.42

C₂H₅OH

2.00930

2.00616

2.00225

0.44

0.48

3.25

1.39

CH₃OH

2.00937

2.00616

2.00228

0.43

0.48

3.24

1.38

H₂O

2.00893

2.00606

2.00225

0.56

3.39

C₆H₅CH₃

2.00928

2.00619

2.00224

0.42

0.51

3.25

1.47

CH₃OH

2.00938

2.00619

2.00221

3.26

1.48

C₆H₅CH₃

2.00927

2.00621

2.00229

3.27

1.43

C₆H₅CH₃

2.00927

2.00622

2.00217

3.28

CH₃OH

2.00937

2.00618

2.00220

3.26

C₆H₅CH₃

2.00924

2.00614

2.00222

3.28

1.36

CH₃OH

2.00936

2.00618

2.00221

3.27

C₆H₅CH₃

2.00929

2.00617

2.00222

3.23

1.39

CH₃OH

2.00940

2.00623

2.00221

3.25

C₆H₅CH₃

2.00927

2.00615

2.00222

3.26

1.38

HM

2.00915

2.00526

2.00217

1.95

3.23

1.45

CH₃OH

2.00940

2.00617

2.00222

3.29

C₆H₅CH₃

2.00913

2.00601

2.00206

3.27

1.46

CH₃OH

2.00932

2.00620

2.00221

3.29

C₆H₅CH₃

2.00931

2.00618

2.00226

0.45

0.52

3.23

1.40

C₆H₅CH₃

2.00928

2.00608

2.00220

0.46

0.50

3.23

1.42

C₆H₅CH₃

2.00918

2.00602

2.00219

0.45

0.52

3.22

1.42

CH₃OH

2.00926

2.00599

2.00214

0.40

0.52

3.25

1.39

C₆H₅CH₃

2.00917

2.00595

2.00234

0.46

0.55

3.21

1.41

CH₃OH

2.00922

2.00596

2.00225

0.44

0.56

3.23

1.41

Имидазолидиновая серия

C₆H₅CH₃

2.00957

2.00624

2.00228

0.57

0.63

3.32

1.51

C₆H₅CH₃

2.00951

2.00620

2.00221

0.51

0.63

3.28

1.47

C₆H₅CH₃

2.00940

2.00623

2.00226

0.62

0.68

3.36

1.55;

C₆H₅CH₃

2.00941

2.00611

2.00226

0.51

0.69

3.46

1.55

C₆H₅CH₃

2.00962

2.00613

2.00211

0.64

0.72

3.29

1.5

C₆H₅CH₃

2.00970

2.00613

2.00213

0.64

0.69

3.35

1.56

C₆H₅CH₃

2.00872

2.00598

2.00211

3.39

CH₃OH

2.00834

2.00598

2.00218

3.57

C₆H₅CH₃

2.00913

2.00597

2.00211

3.28

CH₃OH

2.00923

2.00860

2.00605

2.00215

3.42

C₆H₅CH₃

2.00925

2.00604

2.00221

0.40

0.51

3.26

1.43

HM

2.00901

2.00601

2.00219

3.32

C₆H₅CH₃

2.00910

2.00582

2.00217

3.26

CH₃OH

2.00877

2.00585

2.00216

3.42

HM

2.00898

2.00531

2.00212

3.32

C₆H₅CH₃

2.00905

2.00611

2.00219

0.48

0.51

3.29

1.41

CH₃OH

2.00885

2.00601

2.00220

3.36

HM

2.00905

2.00614

2.00221

3.26

1.51

C₆H₅CH₃

2.00913

2.00606

2.00215

0.45

0.52

3.24

1.43

HM

2.00896

2.00607

2.00217

3.32

Ссылки: О.Я. Гринберг, Диссертация д.ф.-м.н., Москва, 1988; V.I. Krinichnyi, 2-mm Wave Band EPR Spectroscopy of Condensed Systems, CRC Press, Boca Raton, 1995.
Сокращения: ГМАСК - гексаметил-т-амидсерная кислота, НМББА - н-метоксибензилиден-н'-бутиланилин. Ошибки измерения компонент g- и A-тензоров составляют соответственно 7×10^-5 и 3×10^-2 мТл.