6 Group 13–15 Needle-Shaped Oligomers and Nanorods: Structures. . .
231
Table 6.3 Selected M-N bond lengths (Å) and bond angles (deg) of binary oligomers
Parameter (ring number)
[CH 3 MNH] 10
(CH 3 ) 3 [CH 3 MNH] 9 H 3
M=Al
M=Ga
M=In
M=Al
M=Ga
M=In
RM–N
1.939
2.004
2.216
d⊥(1)
1.938
1.998
v2.212
1.968
2.030
2.246
d (1–2)
1.932
1.990
2.203
1.896
1.945
2.15
d⊥(2)
1.933
1.987
2.200
1.951
2.013
2.232
d (2–3)
1.922
1.983
2.193
1.881
1.931
2.13
d⊥(3)
1.943
2.001
2.216
1.968
2.028
2.252
M–NH
1.937
2.001
2.210
φ M (1)
88.1
87.0
90.1
98.9
98.5
97.6
φ M (2)
102.1
102.0
102.0
99.5
99.6
98.8
φ M (3)
103.0
102.8
102.7
99.3
98.5
97.0
φ N (1)
118.6
119.2
121.0
116.6
116.8
117.0
φ N (2)
115.0
115.8
117.8
113.0
113.8
115.6
φ N (3)
89.2
91.0
93.8
117.7
118.5
121.3
θ NMNM (1)
74.5
75.3
76.8
64.6
65.1
65.7
θ NMNM (2)
62.6
61.8
60.8
67.5
66.6
65.7
θ NMNM (3)
83.6
82.5
80.8
63.0
63.0
61.9
θ Me
a
180.0
180.0
180.0
171.2
162.4
156.4
Adapted by permission from Springer Nature: Springer [56], COPYRIGHT (2014)
a θ Me dihedral angle shows rotation of CH 3 group relative to the first ring (see Fig. 6.15), value of
180 ◦ corresponds to C 3v point group
Fig. 6.15 Ring numbering and designation of structural parameters of oligomers. (a)
[CH 3 MNH] 10 ; (b) (CH 3 ) 3 [CH 3 MNH] 9 H 3
this trend holds both for binary and mixed oligomers and it does not depend on the
position of substituted atom.
Overall, we conclude that unlike similar nitrogen clusters [182], optimized
geometry of the Ga-N-based oligomer rod is strongly affected by a type of terminal
231
Table 6.3 Selected M-N bond lengths (Å) and bond angles (deg) of binary oligomers
Parameter (ring number)
[CH 3 MNH] 10
(CH 3 ) 3 [CH 3 MNH] 9 H 3
M=Al
M=Ga
M=In
M=Al
M=Ga
M=In
RM–N
1.939
2.004
2.216
d⊥(1)
1.938
1.998
v2.212
1.968
2.030
2.246
d (1–2)
1.932
1.990
2.203
1.896
1.945
2.15
d⊥(2)
1.933
1.987
2.200
1.951
2.013
2.232
d (2–3)
1.922
1.983
2.193
1.881
1.931
2.13
d⊥(3)
1.943
2.001
2.216
1.968
2.028
2.252
M–NH
1.937
2.001
2.210
φ M (1)
88.1
87.0
90.1
98.9
98.5
97.6
φ M (2)
102.1
102.0
102.0
99.5
99.6
98.8
φ M (3)
103.0
102.8
102.7
99.3
98.5
97.0
φ N (1)
118.6
119.2
121.0
116.6
116.8
117.0
φ N (2)
115.0
115.8
117.8
113.0
113.8
115.6
φ N (3)
89.2
91.0
93.8
117.7
118.5
121.3
θ NMNM (1)
74.5
75.3
76.8
64.6
65.1
65.7
θ NMNM (2)
62.6
61.8
60.8
67.5
66.6
65.7
θ NMNM (3)
83.6
82.5
80.8
63.0
63.0
61.9
θ Me
a
180.0
180.0
180.0
171.2
162.4
156.4
Adapted by permission from Springer Nature: Springer [56], COPYRIGHT (2014)
a θ Me dihedral angle shows rotation of CH 3 group relative to the first ring (see Fig. 6.15), value of
180 ◦ corresponds to C 3v point group
Fig. 6.15 Ring numbering and designation of structural parameters of oligomers. (a)
[CH 3 MNH] 10 ; (b) (CH 3 ) 3 [CH 3 MNH] 9 H 3
this trend holds both for binary and mixed oligomers and it does not depend on the
position of substituted atom.
Overall, we conclude that unlike similar nitrogen clusters [182], optimized
geometry of the Ga-N-based oligomer rod is strongly affected by a type of terminal