Supporting Information
Matrix isolation ESR spectroscopy and magnetic anisotropy of
D3h symmetric septet trinitrenes
Eugenii Ya. Misochko, Alexander V. Akimov, Artem A. Masitov, Denis V. Korchagin,
Sergei M. Aldoshin, and Sergei V. Chapyshev
Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka,
Moscow Region, Russia
Content:
1S. Reassignment of the ESR spectrum of trinitrene 9.
2S. Cartesian coordinates of trinitrenes studied.
1
1S. Reassignment of the ESR spectrum of trinitrene 9.
Trinitrene 9 has been generated in 1968 by the photolysis of the corresponding triazide in
solid 2-methyltetrahydrofuran (2MTHF) solutions at 77 K.1S The experimental ESR spectrum was
not shown in the paper. Authors pointed out four ESR lines at 42, 165, 275 and 632 mT that were
assigned to a series of Z-transitions. Based on this assignment, the parameter D = 0.0548 cm-1 was
determined. The simulated spectrum for a septet molecule with D = 0.0548 cm-1 and E = 0 is
shown in Fig. 1S-a. The low-field EPR line at Hz1 = 42 mT corresponds to the allowed Z-transition
W-3  W-2. The resonance condition for the low-field Z-transition W-3  W-2 is described by the
equation:
h 0  5D  gH z1 .
(1S)
At experimental conditions in Ref. [1S] (0 = 9.396 GHz and Hz1 = 42 mT), the equation (1S) gives
the parameter D equals to 0.055 cm-1. The most intense ESR lines of the spectrum correspond to
the XY-transitions (Fig. 1S-a). Among all allowed Z-transitions, only the low-field Z1 transition at
42 mT is reasonably intense. The other reported Z-lines at 165 (z2), 275 (z3) and 630 (z6) mT are
practically invisible in the spectrum.
1S
E. Wasserman, K. Schueller, and W. A. Yager, Chem. Phys. Lett. 2, 259 (1968).
2
1S-a
1S-b
FIG. 1S. Zeeman energy levels, allowed transitions, and simulated ESR spectra of septet tinitrenes
with D = -0.0548 cm-1, E = 0 (a) and D = -0.092 cm-1, E = 0 (b). The ESR lines at 42, 165, 275 and
632 mT are marked with (*). A denotes the “extra line”. 0 = 9.396 GHz.
If we assign the low-field ESR line at Hz1 = 42 mT to the allowed Z-transition W-2  W-1,
then the resonance condition for this transition is described by the equation:
h 0  3D  gH z1 .
(2S)
This equation gives the parameter D = 0.092 cm-1, which is 1.67 times larger than Dreported in
Ref. [1S]. The simulated spectrum for a septet molecule with D = 0.092 cm-1 is shown in Fig 1S-b.
The spectrum displays four strong lines at 42, 165, 275 and 630 mT reported in Ref [1S]. However,
3
the lines at 165 and 275 mT correspond to the xy1-transition and “extra line”, respectively. Totally,
the spectrum of trinitrene 9 in Fig. 1S-b is very similar to that of trinitrene 5 with D = 0.0957 cm-1,
in which twelve ESR lines were recorded experimentally in this study (see Fig. 2S).
5
FIG. 2S. Zeeman energy levels, allowed transitions, and theoretical ESR spectrum of septet tinitrene
5 with D = -0.0957 cm-1 and E = 0. The ESR lines in the spectrum are marked according to the
notations accepted in the text. A denotes the “extra line”. 0 = 9.107 GHz.
4
3S. Cartesian coordinates of trinitrenes studied.
Method : UB3LYP/6-311G(d)
Charge : 0
Multiplicity : 7
Symmetry : D3h
Total energy: -1773.3823229 a.u.
5
6
6
7
6
7
6
7
6
6
17
17
17
-0.709424000 -1.228758000
-1.447662000
0.000000000
-2.764693000
0.000000000
0.723831000 -1.253712000
1.382346000 -2.394294000
0.723831000
1.253712000
1.382346000
2.394294000
-0.709424000
1.228758000
1.418847000
0.000000000
-1.572400000
2.723477000
3.144801000
0.000000000
-1.572400000 -2.723477000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
5
Method : UB3LYP/6-311G(d)
Charge : 0
Multiplicity : 7
Symmetry : CS
Total energy: -433.8477717 a.u.
6
6
6
6
6
6
6
1
1
6
1
1
1
7
7
7
-1.104779000
-0.375950000
1.033752000
1.748372000
1.033752000
-0.375950000
1.562041000
1.562041000
-2.586710000
-2.903976000
-3.113994000
-2.903976000
3.051498000
-0.994975000
-0.994975000
-0.199179000
-0.075005000
0.167271000
0.290396000
0.167271000
-0.075005000
0.255869000
0.255869000
-0.417730000
-0.961153000
0.544114000
-0.961153000
0.514651000
-0.184420000
-0.184420000
0.000000000
1.237285000
1.229453000
0.000000000
-1.229453000
-1.237285000
2.169220000
-2.169220000
0.000000000
0.890547000
0.000000000
-0.890547000
0.000000000
-2.398004000
2.398004000
6
Method : UB3LYP/6-311G(d)
Charge : 0
Multiplicity : 7
Symmetry : D3h
Total energy: -442.6039851 a.u.
7
6
6
6
7
7
7
7
7
7
0.000000000
1.139589000
-1.139589000
0.000000000
1.206606000
-1.206606000
2.307357000
0.000000000
-2.307357000
1.315884000
-0.657942000
-0.657942000
-1.393269000
0.696634000
0.696635000
-1.332153000
2.664306000
-1.332153000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
7
Method : UB3LYP/6-311G(d)
Charge : 0
Multiplicity : 7
Symmetry : D3h
Total energy: -394.5168243 a.u.
8
6
6
7
6
7
6
7
6
6
1
1
1
-0.712978000
-1.433176000
-2.755426000
0.716588000
1.377713000
0.716588000
1.377713000
-0.712978000
1.425957000
2.507670000
-1.253835000
-1.253835000
-1.234915000
0.000000000
0.000000000
-1.241167000
-2.386269000
1.241167000
2.386269000
1.234915000
0.000000000
0.000000000
-2.171706000
2.171706000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
8
Method : UB3LYP/6-311G(d)
Charge : 0
Multiplicity : 7
Symmetry : D3h
Total energy: -671.2767235 a.u.
9
6
6
7
6
7
6
7
6
6
6
6
6
7
7
7
-0.719137000
-1.448713000
-2.761770000
0.724357000
1.380885000
0.724357000
1.380885000
-0.719137000
1.438275000
-1.425645000
2.851290000
-1.425645000
4.008758000
-2.004379000
-2.004379000
-1.245582000
0.000000000
0.000000000
-1.254622000
-2.391763000
1.254622000
2.391763000
1.245582000
0.000000000
-2.469289000
0.000000000
2.469289000
0.000000000
3.471687000
-3.471687000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
9
Method : UB3LYP/6-311G(d)
Charge : 0
Multiplicity : 7
Symmetry : D3h
Total energy: -8115.1232965 a.u.
10
6
6
7
6
7
6
7
6
6
35
35
35
-0.710048000 -1.229839000
-1.449752000
0.000000000
-2.768948000
0.000000000
0.724876000 -1.255522000
1.384474000 -2.397979000
0.724876000
1.255522000
1.384474000
2.397979000
-0.710048000
1.229839000
1.420095000
0.000000000
-1.651338000
2.860201000
-1.651338000 -2.860201000
3.302676000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
10