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Clam Structures of Metal-Biphenyl Complexes: M-C12H10 (M = Sc, La, Ti)

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Presentation on theme: "Clam Structures of Metal-Biphenyl Complexes: M-C12H10 (M = Sc, La, Ti)"— Presentation transcript:

1 Clam Structures of Metal-Biphenyl Complexes: M-C12H10 (M = Sc, La, Ti)
BRAD SOHNLEIN, YUXIU LEI, and DONG-SHENG YANG Department of Chemistry University of Kentucky Lexington, KY 40506, USA $$ NSF & KSEF $$

2 Structure of Biphenyl Biphenyl is planar in the crystalline state
In the gas phase, the phenyl rings are twisted

3 Structure of Biphenyl Biphenyl is planar in the crystalline state
In the gas phase, the phenyl rings are twisted A balance between p-conjugation and steric repulsions

4 Metal-Biphenyl Complexes
Good models for conducting organometallic polymers Two types of structures have been identified in the condensed phase No gas phase structural determination of M-biphenyl complexes

5 Experimental Apparatus
biphenyl Sc, La, or Ti rod Nd:YAG UV

6 Sc-Biphenyl ZEKE Spectrum
0-0 39114 cm-1 FWHM ~ 8 cm-1 Ta Expt.

7 Sc-Biphenyl ZEKE Spectrum
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta 12 Expt.

8 Theoretical Methodology
B3LYP and B3P86 implemented in Gaussian 03* Geometry optimizations and frequency analyses Calculate Franck-Condon integrals within the harmonic approximation Simulate spectra at finite temperatures using a Boltzman distribution * G(d,p) for all atoms, except La atom (LanL2DZ ECP)

9 Sc-Biphenyl Electronic States
ion 3A 1A Half-sandwich neutral 2A 4A

10 Sc-Biphenyl Electronic States
Clam ion 3A 1A Half-sandwich 2A neutral 4A 2B1

11 Sc-Biphenyl Electronic States
Clam ion 3A 1A Half-sandwich 4B1 neutral 2A 4A 2B1

12 Sc-Biphenyl Electronic States
Clam 3A ion 1A Half-sandwich 1A1 4B1 neutral 2A 4A 2B1

13 Sc-Biphenyl Electronic States
Clam 3B1 3A ion 1A Half-sandwich 1A1 4B1 neutral 2A 4A DS =  1 2B1

14 Sc-Biphenyl Electronic States
Clam 3B1 3A ion 1A Half-sandwich 1A1 neutral DS =  1 xxxxxxxxxxxxxxxxxxxxx 2B1

15 Sc-Biphenyl Electronic States
Clam 3B1 ion 1A1 ~ cm-1 neutral DS =  1 xxxxxxxxxxxxxxxxxxxxx 2B1

16 Sc-Biphenyl Electronic States
Clam 3B1 3A ion 1A Half-sandwich 1A1 4B1 neutral 2A 4A DS =  1 xxxxxxxxxxxxxxxxxxxxx 2B1

17 Sc-Biphenyl ZEKE Spectrum
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta Expt. Half-sandwich

18 Sc-Biphenyl ZEKE Spectra
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta Expt. Half-sandwich * 3A  4A

19 Sc-Biphenyl ZEKE Spectra
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta Expt. Half-sandwich 3A  2A * 3A  4A

20 Sc-Biphenyl ZEKE Spectra
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta Expt. 1A  2A Half-sandwich 3A  2A * 3A  4A

21 Sc-Biphenyl ZEKE Spectra
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta Expt. Clam (C2v)

22 Sc-Biphenyl ZEKE Spectra
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta Expt. Clam (C2v) 3B1  4B1

23 Sc-Biphenyl ZEKE Spectra
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta Expt. Clam (C2v) 3B1  2B1 3B1  4B1

24 Sc-Biphenyl ZEKE Spectra
568 39114 cm-1 FWHM ~ 8 cm-1 378 336 284 Ta Expt. 1A1  2B1 Clam (C2v) 3B1  2B1 3B1  4B1

25 Observed Transition and Vibrations (cm-1)
Expt. Theo.

26 Sc-Biphenyl Vibration Movies
n17+ = 336 cm-1 n16+ = 378 cm-1 n15+ = 568 cm-1 n32+/ n32 = 142 / 155 cm-1

27 Further Experiments Is forming a clam structure dependent on:
a.) size of metal—down the group b.) electronic species—across the row La-bp (size effect) and Ti-bp (electronic effect)

28 La-Biphenyl ZEKE Spectrum
0-0 36516 cm-1 FWHM ~ 6 cm-1 Expt.

29 La-Biphenyl ZEKE Spectrum
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 Expt.

30 La-Biphenyl Vibration Movies
n17+ = 257 cm-1 n16+ = 370 cm-1 n15+ = 532 cm-1 Not observed

31 Sc-Biphenyl Electronic States
Clam 3B1 3A ion 1A Half-sandwich 1A1 4B1 neutral 2A 4A DS =  1 2B1

32 La-Biphenyl Electronic States
Clam 3B1 3A 1A ion Half-sandwich 1A1 4B1 neutral 2A DS =  1 4A 2B1

33 La-Biphenyl Electronic States
Clam 3B1 3A 1A ion 1A1 ~ cm-1 neutral DS =  1 xxxxxxxxxxxxxxxxxxxxx 2B1

34 La-Biphenyl Electronic States
Clam 3B1 3A 1A ion Half-sandwich 1A1 4B1 neutral 2A DS =  1 4A xxxxxxxxxxxxxxxxxxxxx 2B1

35 La-Biphenyl ZEKE Spectrum
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 Expt. Half-sandwich

36 La-Biphenyl ZEKE Spectra
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 Expt. Half-sandwich 3A  4A

37 La-Biphenyl ZEKE Spectra
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 Expt. Half-sandwich 3A  2A 3A  4A

38 La-Biphenyl ZEKE Spectra
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 Expt. 1A  2A Half-sandwich 3A  2A 3A  4A

39 La-Biphenyl ZEKE Spectrum
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 Expt. Clam (C2v)

40 La-Biphenyl ZEKE Spectra
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 Expt. Clam (C2v) 3B1  4B1

41 La-Biphenyl ZEKE Spectra
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 Expt. Clam (C2v) 3B1  2B1 3B1  4B1

42 La-Biphenyl ZEKE Spectra
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 La Expt. 1A1  2B1 Clam (C2v) 3B1  2B1 3B1  4B1

43 La-Biphenyl ZEKE Spectrum
36 % narrower 5.5 3.5

44 La-Biphenyl ZEKE Spectra
257 36516 cm-1 370 FWHM ~ 6 cm-1 532 * La Expt. 1A1  2B1 Clam (C2v) 3B1  2B1 3B1  4B1

45 Further Experiments Is forming a clam structure dependent on:
a.) size of metal—down the group b.) electronic species—across the row La-bp (size effect) and Ti-bp (electronic effect) Sc and La: (n-1)d1 ns2 Ti: (n-1)d2 ns2

46 Ti-Biphenyl ZEKE Spectrum
Expt.

47 Ti-Biphenyl ZEKE Spectrum
194 Expt.

48 Ti-Biphenyl ZEKE Spectrum
350 194 Expt.

49 Ti-Biphenyl ZEKE Spectrum
350 194 194 Expt.

50 Ti-Biphenyl ZEKE Spectrum
350 194 326 194 Expt.

51 Ti-Biphenyl ZEKE Spectrum
350 194 326 Expt. 208 194 Expt.

52 Ti-Biphenyl ZEKE Spectrum
350 194 326 208 194 43842 0-0 350 Expt.

53 Ti-Biphenyl Electronic States
Clam 2A ion Half-sandwich 4A 1A neutral 5A 3A

54 Ti-Biphenyl Electronic States
Clam 2A ion Half-sandwich 4A 1A neutral 5A 3B1 3A 1A1

55 Ti-Biphenyl Electronic States
Clam 2A 4B1 clam ? ion 2B1 Half-sandwich 4A 5A DS =  1 1A neutral 5A 3B1 3A 1A1

56 Ti-Biphenyl Electronic States
Clam 2B1 ion 46700 cm-1 DS =  1 xxxxxxxxxxxxxxxxxxxxx neutral 1A1

57 Ti-Biphenyl ZEKE Spectrum
350 194 326 208 194 43842 350 Expt.

58 Ti-Biphenyl ZEKE Spectra
350 194 326 208 194 43842 350 Expt. 2B1  1A1

59 Ti-Biphenyl Vibration Movies
n18 +/n18 = 194 / 208 cm-1 n17+/n17 = 350 / 326 cm-1

60 Summary 11 % overestimation

61 IE Overestimation by B3P86
Average ~ 10 % bz = benzene, np = naphthalene, phnp = phenyl-naphthalene, bp = biphenyl

62 Summary 10 % correction

63 Summary 10 % correction

64 Conclusions A new “clam” binding mode for biphenyl was identified
Small (Sc) and large (La) metal atom coordination Different electron configurations: (n-1)d1 ns2 and (n-1)d2 ns2 Recorded first vibronic spectrum of a gas phase metal-biphenyl complex AIE measurements Metal- and ligand-based frequencies B3P86 overestimates IEs by ~ 10%

65 Thanks for your time

66 Size-dependent? Bond lengths: Increased radius by ~ 16 %
Sc-Sc = Å / 2 = Å La-La = Å / 2 = Å Increased radius by ~ 16 % clam still formed What about Ti? Ti-Ti = / 2 Å = Å valence electon configuration 4s23d2 CRC Handbook of Chemistry, 66th edition © 1985

67 La-biphenyl ZEKE spectrum
257 36516 cm-1 ~ 3.5 370 FWHM ~ 6 cm-1 532 La Expt. ~ 5.5 ~ 5.3 ~ 5.2

68 La-biphenyl ZEKE spectrum
36516 cm-1 ~ 3.5 FWHM ~ 6 cm-1 Expt. ~ 5.5 ~ 5.3 ~ 5.2

69 La-biphenyl ZEKE spectrum
5.5 3.5

70 Observed transition and vibrations (cm-1)
IE overestimated by 13 % Expt. Theo.

71 Ti-biphenyl ZEKE spectrum
FWHM ~ 15 cm-1 Expt.

72 Ti-biphenyl ZEKE spectrum
194 FWHM ~ 15 cm-1 Expt.

73 Ti-biphenyl ZEKE spectrum
350 194 FWHM ~ 15 cm-1 Expt.

74 Ti-biphenyl ZEKE spectrum
350 194 FWHM ~ 15 cm-1 194 Expt.

75 Ti-biphenyl ZEKE spectrum
350 194 FWHM ~ 15 cm-1 326 194 Expt.

76 Ti-biphenyl ZEKE spectrum
350 194 FWHM ~ 15 cm-1 326 194 208 Expt.

77 Ti-biphenyl ZEKE spectrum
350 194 FWHM ~ 15 cm-1 326 194 208 0-0 350 Expt. 43842 cm-1

78 Ti-biphenyl ZEKE spectrum
350 43842 cm-1 194 326 194 208 350 Expt. 4A  5A

79 Ti-biphenyl ZEKE spectrum
350 43842 cm-1 194 326 194 208 350 Expt. 4A  3A 4A  5A

80 Ti-biphenyl ZEKE spectrum
350 43842 cm-1 194 326 194 208 350 Expt. 2A  3A 4A  3A 4A  5A

81 Ti-biphenyl ZEKE spectrum
350 43842 cm-1 194 326 194 208 350 Expt. Clam 2B1  3B1 2A  3A 4A  3A 4A  5A

82 Ti-biphenyl ZEKE spectrum
350 43842 cm-1 194 326 194 208 350 Expt. Clam 2B1  1A1 2B1  3B1 2A  3A 4A  3A 4A  5A

83 Ti-biphenyl ZEKE spectrum
350 43842 cm-1 194 326 194 208 350 Expt. Clam 2B1  1A1 2B1  3B1 2A  3A 4A  3A 4A  5A

84 Observed transition and vibrations (cm-1)
IE overestimated by 6 % Expt. Theo.

85 Observed transition and vibrations (cm-1)
IE overestimated by 6 % Expt. Theo.

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