Pentaatomic planar tetracoordinate carbon molecules [XCAl q … · 2010. 9. 20. · Pentaatomic...

Supplementary Material (ESI) for PCCP This journal is © the Owner Societies 2010

Pentaatomic planar tetracoordinate carbon molecules [XCAl3]q [(X,q)=(B,-2),

(C,-1), (N,0)] with C−X multiple bonding

Supporting Information.

Zhong-hua Cui, Chang-bin Shao, Si-meng Gao and Yi-hong Ding*

State Key Laboratory of Theoretical and Computational Chemistry, Institute of

Theoretical Chemistry, Jilin University, Changchun 130023, People’s Republic of

China

SI1: The structures and their relative energies of the isomer and transition of

[XCAl3]q; [(X, q)=(B, -2), (C, -1), (N, 0)].

SI2: Low-lying counterion-stabilized species structures of Na+[C2Al3]−,

Na+[BCAl3]2−, (Na+)2[BCAl3]2−and Mg2+[BCAl3]2− molecules.

SI3: The details of MD simulations.

SI4: Calculated molecular properties of [XCAl3]q; [(X,q)=(B,-2), (C,-1), (N,0)]

(pptC) structures.


SI1-Figure 1~3. Calculated structures and relative energies for the isomer of the

[BCAl3]2−, [C2Al3]− and [NCAl3], respectively. The parentheses and square bracket

values obtained at the CCSD(T)/6-311+G(2df)//B3LYP/6-311+G(d) and

B3LYP/6-311+G(d) levels, respectively. The energy values are in kcal/mol, bond

lengths are in angstroms, bond angles in degrees.

SI1-Figure 4~6. Optimized geometries of interconversion transition states of

[BCAl3]2−, [C2Al3]− and [NCAl3] at the B3LYP/6-311+G(d) level, respectively. The

parentheses and square bracket values obtained at the

CCSD(T)/6-311+G(2df)//B3LYP/6-311+G(d) and B3LYP/6-311+G(d) levels,

respectively. The energy values are in kcal/mol, bond lengths are in angstroms, bond

angles in degrees.


SI1-Figure 1

B-02 Cs[2.7] [24.3]

[24.4]

[70.3]

[131.4]

[33.0]

[53.5] [58.2]

[73.1] [75.7]

(0.8) (5.1) (26.4)

(35.7)

(79.6)

(51.3)

(39.3)

(56.1)

(65.6) (77.0)

[33.3]

[135.0]

[115.6]

[56.2]

[74.9]

[131.7]

(46.1) (60.2)

(77.9)

2.265 2.104

2.098 1.90937.4

85.7 92.12.069

2.232

97.4

2.284144.8

57.3

1.460

1.420

2.2811.932

2.94955.3

94.2

59.9

1.858 1.379 2.082 2.611

2.071

1.378

1.870 2.647 1.4031.8162.696

152.8

1.854 1.824 2.054 2.070

2.644 1.838 1.832 2.173 1.892 2.494 1.999 2.064

2.592 2.008 2.021 1.904

1.4041.9792.680

176.9150.9Al4Al3B2C1=-106.9Al5Al3B2C1=106.9

1.9982.014

2.5511.891

153.7175.9

89.2

1.9712.082

1.8431.852

91.0

157.5179.11.924

1.922

2.1402.045

89.2

51.083.6

B4Al2Al3C1=146.1Al5B4Al3Al2=-164.1

1.872

1.394

2.463

2.68263.5

126.0

82.9

2.210

1.399 1.902 2.622

176.2109.6

66.2

2.193

2.227

1.994

1.875

73.247.0

104.6

C4Al3Al2B1=-150.0Al5C4Al3Al2=-175.6

Al1

Al4Al5

Al2

Al3

Al4

Al3Al4

Al5

Al1 Al4 Al5

Al1

Al4 Al5

Al1 Al4 Al5Al1

Al4 Al5

Al2

Al3

Al5

Al3

Al4

Al5

Al1 Al2

Al5

Al4

Al1 Al2 Al4 Al2 Al3 Al5 Al1 Al3Al4

Al1 Al3

Al4

Al5

Al3Al1 Al3

Al5

Al2

Al3

Al5

C3

C5

C2

C2 C3

C3

C2

C4

C2

C1

C4

C1 C2

C5

C1C3

C5

B2

B1

B1

B3B2

B1

B1

B3

B2

B4

B2

B2 B4

B2

B4B5

B3

[-1.6]B-03 Cs B-04 Cs

B-08 Cs

B-10 Cs B-11 C1 B-12 C2V

B-15 CsB-14 CsB-13 C1

B-19 Cs

B-20 Cs

[23.5](31.4)

1.867

1.3922.195

135.5

Al4B3C2Al1=120.9Al5B3C2Al1=-120.9

178.7 Al1

Al4

Al5C2

B3

B-06 Cs[30.1](30.8)

1.404

1.9402.119

2.71556.2

86.4

80.7

Al4B2Al3C1=152.8Al5Al4Al3B2=-131.9

Al3Al4

Al5

C1B2

B-05 C1 B-07 C∞

B-16 C∞

B-09 C∞

B-17 C∞ B-18 C∞

179.97 179.99 179.99

[0.0](0.0)

1.465

1.920

2.044

104.6Al3

Al4

Al5

C1B2

B-01 C2V


SI1-Figure 2

1.96334.4

2.175

90.4

1.342

1.929

111.9

2.088

1.2701.937

92.42.694

78.6

128.8

1.2611.8382.632

152.7

1.858

1.844

141.1

168.9 1.8741.842

149.4

1.904

1.935

145.4

3.11833.8

1.911 2.5251.809

119.1

166.6

2.116

C

Al

1

2

345

11

1

2

2

23

3

3

4

4

4

5

5

5

2.077

1.279 73.0

1.966

95.8

2.839

55.3

D4312=167.5D5413=-147.0

C-02 C2vC-01 C2v C-03 C1

C-05 Cs C-07 C2vC-06 C2v

1.2681.979

71.32.648147.5

D4312=122.1

2.409

63.0D5431=143.4

C-08 C1

1.928

1.935

89.0

1.940

46.8

D4321=142.51.884

106.6

D5423=-174.0

C-09 C2v

1.9502.196

88.287.6

42.6D4132=87.7D5432=54.5

2.651 1.801 1.834 1.937

C-13 Cs

C-12 C2vC-11 C2hC-10 C2v

C-14 Cs

179.5 179.4 179.9

1.930 1.250 1.9302.620

179.4 177.8 158.1

C-04 Cs

(0.0)(3.5) (26.0) (42.7)

(40.7) (38.7) (44.2)

[0.0][4.0] [26.3] [34.3]

[37.6] [43.0] [44.7] [83.0]

[89.2] [99.7] [100.0] [104.4]

[154.0] [161.1]


SI1-Figure 3

N-01 C2V N-02 Cs[0.0](0.0)

[0.5](0.4)

[3.8](4.0)

[13.1](16.9)

[13.0](7.0)

[15.0](12.5)

[12.5](6.8)

[20.3](20.2)

[59.0] [63.6]

[68.3] [68.0] [69.4] [78.0]

[154.8][123.4]

[31.9]

[153.4]

(38.1)

1.279

1.991

2.210116.2 2.254 2.196

2.041 1.93831.9

92.791.7

1.2892.158

1.897

110.01.1801.834

2.563

151.7

1.1601.9542.557

151.6

1.203

2.0582.023

2.679 95.8

78.9

81.81.852

1.2182.090

144.4

1.213

2.2581.912

2.939 99.2

69.6

100.02.014

1.2132.077

142.4

1.8271.8791.936

91.8132.2

80.6

1.757

1.761

1.9551.842

89.788.5

52.8

1.9102.088

1.962

91.388.2

42.2

2.095

1.746

1.832

2.948

1.750

101.5

53.9

47.51.812

1.8811.709

1.749107.7

167.9

153.2

1.8311.884

1.7091.759

109.9

175.6149.0

1.834

1.833

2.5181.735107.6

164.1

176.21.935 2.587 1.683 1.785

180.0 180.0 179.9 1.767 1.823 1.814 2.801

179.7 177.2 177.5

Al3

Al4

Al5

Al1

Al4 Al5

Al3

Al4

Al5 Al3

Al4

Al5

Al3

Al4

Al5

Al3Al4

Al5

Al1

Al4

Al5

Al3Al4

Al5

Al1

Al4

Al5

Al3

Al2

Al5

Al2

Al3

Al5

Al2 Al3

Al4

Al2

Al3

Al4

Al1

Al3

Al5 Al5Al3Al1

Al1Al3

Al4Al2 Al3 Al5 Al2 Al4 Al5

C1C2

C2 C1

C2

C2C3

C1

C2C1

C4

C1

C5C2 C2

C2

C1 C3

N2

N3

N1 N2

N1

N1

N2

N2

N3N4

N1

N5

N1N4

N4

N5

N4 N1

Al4C2Al3N1=159.4Al5Al4C2Al3=50.4

Al4N2Al3C1=176.2Al5Al4N2Al3=12.4

N4Al3C1Al2=-25.0Al5N4Al3C1=-151.4

Al4C1Al3Al2=-91.3N5Al2Al3C1=97.7

Al4C3Al2N1=-174.9Al5Al4C3Al2=170.3

N-03 C2V N-04 C2V

N-05 C2V N-07 C1

N-09 C1

N-08 C2V

N-10 C2V N-11 Cs N-12 Cs

N-13 C1 N-16 CsN-15 CsN-14 Cs

N-19 CsN-17 Cs N-18 C1

C1

Al4

N2

Al3

1.214

2.091

3.0982.485

82.2

44.953.6

Al4Al3C1N2=145.9Al5Al4C1Al3=-101.6

Al5

(12.4)[15.1]

N- 06 C1


SI1-Figure 4

[73.4][34.9]

[84.3]

[76.0][120.0]

[76.2]

(66.7)

(78.4)

(79.8)(73.4)

(34.4)

Al2 Al3

Al4

1.910

1.917

2.1432.068

81.7 83.796.6

Al4C1Al2B3=-27.3Al5B3Al4C1=163.1

1.4022.091

2.6282.775

79.2

60.579.5

Al4Al3C2B1=143.1Al5Al4Al3C2=38.2

1.9362.732 1.936

2.155

76.9 76.9

47.2 Al4C1Al3Al2=-92.0B5Al2Al3C1=112.0

1.9812.063

1.8381.855

179.4

165.1

107.7

2.169

1.849

1.860 2.629

179.7177.6

105.7

Al4C3Al2B1=-178.8Al5Al4C3Al2=-2.4

1.399

1.9692.668

2.487 63.3

151.3

134.1Al4Al3B2C1=-168.9

Al5Al4Al3B2=-162.1

Al2

Al4

Al5

Al3

Al4

Al5

Al1

Al5

Al3

Al2Al4 Al5

Al4

Al5

Al3

C1C2

C1

C3

C4

C1

B3

B1

B5

B2

B1

B2

[133.9]

1.876

2.4882.0242.070

178.9 170.4

115.5

B4Al3Al2C1=-180.0Al5B4Al3Al2=-0.0

C1

Al2Al3B4Al5

B-Ts04/10

B-Ts03/13B-Ts02/04

B-Ts11/13 B-Ts14/16

B-Ts08/17

B-Ts16/18

B-Ts10/15

[15.1](19.9)

2.9312.204

2.0581.914

112.4

38.6

46.2

B4Al2C3Al1=-179.7Al5B4C3Al2=156.3

Al1

Al2

Al5

C3 B4

B-Ts01/02

[58.8](57.4)

1.905

1.400

2.645

2.611

78.7

93.4

61.3 Al4Al1C2B3=166.5Al5Al4Al1C2=144.1

Al1

Al4Al5

C2

B3

[8.0](12.6)

3.078

2.0971.880

2.039

38.4

47.7

124.4 C4Al2B3Al1=-179.8Al5C4B3Al1=-170.7

Al1

Al2

Al5

C4 B3

B-Ts02/03

[55.0](51.9)

1.398

2.184

2.545

2.62262.7

58.2

97.8

Al4Al1B2C3=169.1Al5Al4Al1B2=150.0

Al1

Al4Al5

C3

B2

B-Ts05/10

1.870

177.81.401

121.8

2.202

2.678

51.5

Al4B3C2Al1=116.1Al5Al4B3C2=151.8

Al1

C2

B3

Al4Al5

B-Ts02/06

[56.8](59.3)

1.406

1.8222.7022.470 62.8

151.3

133.8

Al4Al3C2B1=-107.8Al5Al4Al3C2=159.9

Al3

Al4

Al5C2

B1

B-Ts10/12

[134.6]

1.992

2.035

2.542

1.85887.5

145.3

119.6Al1

Al3Al4

C5

B2

B-Ts14/19

[83.5](85.8)

2.137

2.072

1.8491.864

84.8127.7176.5

C4Al3B2Al1=-55.9Al5C4Al3B2=122.4

Al1

Al3Al5 C4

B2

B-Ts11/14

[38.8](39.7)

2.1071.387

1.918

2.830

89.3112.5

56.8

Al4C3B2Al1=-59.5Al5Al4Al1B2=136.9

Al1

B2

C3

Al4Al5

B-Ts04/05

[85.2](78.0)

1.880

1.865

2.0122.076

99.5 116.4 84.8

B4Al3C2Al1=-34.6Al5B4Al3C2=-173.1

Al1

Al3Al5

C2

B4

B-Ts13/14

[34.8](43.0)

B-Ts06/07

[38.4](48.7)

2.025

1.377

1.902 2.647107.3

173.6 177.0

Al1

Al4 Al5C3B2

B-Ts08/09

[140.9]

1.880

2.016

2.0562.606 104.5

172.9175.2

Al4B3Al2C1=-170.4Al5Al4B3Al2=-47.7

Al2Al4Al5

C1

B3

B-Ts07/20

[40.6]

2.6861.9321.407

2.25863.3

96.9

100.3Al4C3Al1B2=180.0Al5Al4C3Al1=180.0

Al1

Al4

Al5

C3B2

(46.5)

B-Ts01/08[63.8](58.8)

2.124

2.143

1.9371.901

90.678.4

90.6

Al4B1Al2C3=-26.7Al5C3Al4B1=161.3

Al2

Al4

Al5 C3

B1

B-Ts01/11

2.482

2.109

1.3881.856

176.7 161.7

91.7

C4B3Al2Al1=180.0Al5C4B3Al2=0.1

Al1

Al2Al5 C4B3

*[23.5]


SI1-Figure 5

C-Ts04/05 Cs

C-Ts02/03 C1

C-Ts05/14 Cs C-Ts06/07 CsC-Ts03/06 C1

C-Ts01/02 C1

C-Ts08/12 Cs

C-Ts03/04 C1

C-Ts11/13 Cs

C-Ts10/13 CsC-Ts08/09 C1 C-Ts08/10 C1

C

Al

123

4

5

1.9471.901150.6

1.873

115.6

1.936

93.6

1

23

4

51.943

1.324120.61.940

94.32.076

164.0

D4213=179.7D5342=180.0

1

23

4 5

1.924

1.26679.4

2.650157.6

2.587

58.6

D4123=67.2D5413=-45.0

12

3

45

1.265

1.839

2.638

2.412

117.1

155.662.8

1

2345

1.889

1.842

1.8422.650

179.3176.6

93.2

1

2 34

5

2.865 2.60982.5

2.01462.21.986

87.8

D4213=-44.7D5312=56.3

1

234

5

1.929

1.258

111.7

174.9

1.975

2.665132.5

1

2 3 4

5

1.928

1.257

114.2

178.11.975

2.662131.0

D4321=179.7D5432=-179.7

1

23

4

51.859

2.517 1.821

1.856160.4

117.1116.6

1

2 3 4

5

1.872

2.518

1.821

1.853

111.9 177.8

120.5

12

34

5

2.305 1.9431.943

1.956

85.088.6

46.1 D4132=85.1D5432=56.3

1

2

345

1.928

1.856

1.841

1.88993.6

174.9

104.1

D4312=136.6D5432=135.8

(16.6)

(48.6) (44.4)

(32.9)

(45.0)

(45.0)

[107.8]

[14.8]

[51.7] [46.7]

[40.8]

[41.2]

[34.3]

[172.3]

[156.9]

[157.4][89.2] [108.5]

C-Ts01/08 C1

1

23

451.918

1.917102.2

1.9501.902

41.1

93.4

D4132=136.8D5431=-175.6

[85.7]


SI1-Figure 6

[8.6](9.4)

1.987

2.2082.064

1.917127.0

34.4

98.8Al1

Al3

Al5

C2N4

N-Ts01/02[18.3](18.6)

1.220

2.249 2.082

2.049Al4C2Al3N1=-160.8Al5C2Al4Al3=149.9

89.478.0

81.6N1

Al3

Al4

Al5 C2

N-Ts01/06[69.6](60.8)

1.9421.969

1.807

1.962

152.0

65.8

100.9

Al4C2Al1Al3=-150.9N5Al4C2Al1=131.8

Al1

Al3

Al4C2

N5

N-Ts01/12[8.9]

(10.3)

2.090

2.069 114.31.884

35.02.145

98.3Al1

Al3

Al5

C4 N2

N-Ts02/03

[29.6](27.8)

1.192

2.201

2.5623.021

78.087.094.1

Al4Al3C1N2=-39.2Al5Al4Al3C1=56.8

Al3

Al4

Al5

C1N2

N-Ts02/09

2.0211.213

2.115

2.61749.9

136.1

176.6Al4N3C2Al1=88.6Al5Al4N3C2=163.7

Al1C2N3

Al4

Al5

N-Ts02/10

(38.0)[67.1]

1.934

1.917

1.8971.83764.0

111.1

103.0

N4Al3C2Al1=-25.3Al5N4Al1C2=152.9

Al3Al5

Al1

C2

N4

N-Ts03/11[26.9](19.9)

1.175 2.018

2.564 2.43461.8

133.1

86.6

Al4Al1N3C2=-148.8Al5Al4Al1N3=-152.4

Al1

Al4 Al5

C2N3

N-Ts04/05

(24.7)

1.182

1.880

2.602

2.91764.7

Al4Al3N2C1=71.7Al5Al3Al4N2=-115.9

173.6

81.2

Al3 Al4

Al5

C1

N2

N-Ts04/09[26.1]

C1

Al4

N2

Al3

Al4Al3C1N2=147.6Al5Al4Al3C1=46.1

Al5

1.209 81.8

2.072

58.7

2.7782.54876.2

N-Ts06/07

(12.4)

N-Ts06/08

(20.7)

[126.4]

[84.1][83.6]

[68.3]

[79.4]

[156.3]

Al2 Al3

Al4

C1

N5

1.816

1.902

97.1

127.8

1.725

100.3 1.747

N4Al3C2Al1=-180.0Al5N4Al3C2=0.0

1.922

1.8821.729

1.784

104.1

112.5

148.3

N4Al3C2Al1=-0.0Al5N4Al3C2=-180.0

1.911

90.4 87.7

2.0352.172

1.84442.4

Al4C1Al3Al2=-91.5N5Al2Al3C1=105.8

1.767 1.884

1.847

2.690

56.1

43.594.5

Al4Al3Al1C2=136.4N5Al1Al4Al3=165.6

1.882

2.583

1.688 1.773111.6

176.2 170.6N4Al3Al2C1=179.9Al5N4Al3Al2=-0.0

1.831

1.842168.2

1.723126.4107.4

2.493

Al1

Al3

Al5

Al1

Al3

Al5

Al1

Al3Al4

Al2 Al3

Al1

Al3Al4

C2

C2C2

C1

C2

N4

N4N5

N4N5

Al5

1.761 2.932 2.829

1.853

110.3 142.5

37.5

C4Al3Al2N1=147.0Al5Al3Al2N1=2.0

N1

Al2 Al3

C4

Al5

N-Ts12/14N-Ts11/15

N-Ts11/13

N-Ts12/16

N-Ts15/19N-Ts14/17

N-Ts11/18[156.7]

Al5

Al4

N2

Al1

C3

1.903

1.229

116.12.103

2.448 54.4144.4

Al4C3N2Al1=91.7Al5Al4C3N2=177.9

[32.1]

[15.5] [19.9]


SI2-Table 1~4. The structures and relative energies for low-lying isomers of

Na+[C2Al3]−, Na+ [BCAl3]2−, (Na+)2[BCAl3]2− and Mg2+[BCAl3]2− at the

B3LYP/6-311+G(d). Single-point calculations for the low-lying isomers at the

CCSD(T)/6-311+G(2df)//B3LYP/6-311+G(d) level. The relative energy values (ΔE)

are in kcal/mol.


SI2-Table 1.

Na+[C2Al3]− B3LYP/6-311+G(d) ΔE CCSD(T)/6-311+G(2df)//B3LYP/6-311+G(d) ΔE 01 -965.832999 0.0 -963.8725942 0.0 02 -965.8316392 0.9 -963.8716098 0.6 03 -965.8320355 0.6 -963.8678769 3.0 04 -965.8281077 3.1 -963.8632199 5.9

01 Al,0,0.,2.5609065278,0.3031394279

Al,0,0.,-2.5609065278,0.3031394279 C,0,0.,0.6515396918,-0.2657966055 Al,0,0.,0.,1.8090792025 C,0,0.,-0.6515396918,-0.2657966055 Na,0,0.,0.,-2.5678904773

02 C,0,-0.44600442,0.65282595,0.

Al,0,-2.1061999,-0.64379837,0. C,0,0.01885332,-0.59017769,0. Al,0,0.71157564,-2.43816384,0. Al,0,1.73723874,0.54650229,0. Na,0,-0.17191651,2.96228086,0.

03

C,0,-1.13106686,-0.14298698,0. Al,0,1.0399603,-0.2541049,0. C,0,-0.76922327,-1.36921785,0. Al,0,0.23416429,-3.103525,0. Al,0,-1.56234394,1.75366069,0. Na,0,1.37714476,2.72043898,0.


04 Al,0,1.19008209,-1.82253057,0.

Al,0,-0.38647229,1.90348458,0. C,0,-0.72313675,-1.295904,0. C,0,-0.23477685,-0.06433807,0. Al,0,-2.45631638,-0.2267274,0. Na,0,2.47771218,0.91271447,0.


SI2-Table 2 Na+[CBAl3]2― B3LYP/6-311+G(d) ΔE CCSD(T)/6-311+G(2df)//B3LYP/6-311+G(d) ΔE 01 -952.6285527 0.0 -950.6790271 0.0 02 -952.6252952 2.0 -950.671561 4.7 03 -952.6204914 5.1 -950.6699927 5.7 04 -952.6214533 4.5 -950.6697465 5.8 05 -952.6217607 4.3 -950.6669196 7.6 06 -952.6210016 4.7 -950.6659539 8.2 07 -952.621378 4.5 -950.6656635 8.4 08 -952.6153923 8.3 -950.664556 9.1

01

Al,0,2.144895832,-1.0137112145,0. Al,0,-0.7626408381,-1.5767339899,0. Al,0,1.2938314552,1.8730690985,0. C,0,0.4717983674,-0.0091743653,0. B,0,-0.6820775572,0.8519812417,0. Na,0,-3.1173180394,0.4679775895,0.

02

C,0,-0.4669386849,-1.3532036934,0. Al,0,1.3940940679,-1.8473518338,0. Al,0,-2.3071263242,-0.6398897305,0. Al,0,-0.7346129134,2.0625603516,0. B,0,-0.1313860274,0.04178998,0. Na,0,2.266526162,1.2182448961,0.

03

C,0,0.7200165362,0.2171932223,0. Al,0,2.526024782,-0.447745479,0. Al,0,-2.7052368827,-0.2655243312,0.


Al,0,-0.0814191397,-1.7406133899,0. B,0,-0.6942593042,0.3802317225,0. Na,0,0.2462593384,2.5950681653,0.

04

Al,0,0.3143568735,-1.7217214405,0. Al,0,2.4858727209,0.0804125254,0. Al,0,-1.169241658,1.6938259396,0. C,0,0.3415279905,0.2149441028,0. B,0,0.9207919833,1.5412900368,0. Na,0,-2.5587330102,-0.9021575341,0.

05

Al,0,1.8926337782,1.2518177298,0. C,0,-0.9589862682,-0.628295464,0. Al,0,-0.9543805901,1.4662845098,0. Al,0,-2.855266333,-0.8872428464,0. B,0,0.4091941074,-0.3210383071,0. Na,0,2.6008208858,-1.6863122021,0.

06

C,0,0.0762316218,1.1753906014,0. Al,0,-1.7944548256,1.5392250283,0. Al,0,3.1510407134,-0.3191440156,0. Al,0,0.2693185183,-0.88323773,0. B,0,1.4649365671,0.9898506809,0. Na,0,-2.6322590351,-1.499319565,0.

07


C,0,1.2867301641,-0.7097612013,0. Al,0,3.1174476883,-0.1357869549,0. Al,0,-2.1049998135,-1.5177027751,0. Al,0,0.4860380769,1.1685866939,0. B,0,-0.0600052293,-1.0888599315,0. Na,0,-2.4795180565,1.513102149,0.

08 C,0,0.6777017979,0.3130773128,0.

Al,0,0.5960119421,2.2735304287,0. Al,0,-0.1114688534,-1.6252728896,0. Al,0,-2.776812814,-0.1766927293,0. B,0,-0.7611635149,0.4300412828,0. Na,0,2.6909687923,-0.9108006653,0.


SI2-Table 3 (Na+)2[CBAl3]2― B3LYP/6-311+G(d) ΔE CCSD(T)/6-311+G(2df)//B3LYP/6-311+G(d) ΔE 01 -1114.9116513 0.0 -1112.5312561 0.0 02 -1114.9100098 1.0 -1112.5292324 1.3 03 -1114.9033718 5.2 -1112.5233931 4.9 04 -1114.902835 5.5 -1112.521527 6.1 05 -1114.9027882 5.6 -1112.521366 6.2 06 -1114.8970464 9.2 -1112.5137537 11.0 07 -1114.9002565 7.2 -1112.5125249 11.8 08 -1114.8982815 8.4 -1112.5124858 11.8 09 -1114.8941444 11.0 -1112.5102597 13.2

01 Al,0,-1.2874121561,1.5606318141,0.

Al,0,1.5980087366,1.5211731666,0. Al,0,-0.8068713555,-1.6566956012,0. C,0,0.0525267591,0.1785154474,0. B,0,1.158428817,-0.7383792992,0. Na,0,3.600673194,-0.9522261761,0. Na,0,-3.5591543252,-0.4891350616,0.

02

Al,0,0.,0.,-2.6512163474 Al,0,0.,-1.9950113313,-0.6354626294 Al,0,0.,1.9950113313,-0.6354626294 C,0,0.,0.,-0.6618583669 B,0,0.,0.,0.7730321236 Na,0,0.,-2.0447339544,2.3264023947 Na,0,0.,2.0447339544,2.3264023947

03

C,0,-0.9193134434,0.3342084875,0.


Al,0,-0.1067429135,2.1175625686,0. Al,0,-1.0960186779,-1.6946698322,0. Al,0,1.8163598376,-1.7717197788,0. B,0,0.4421108215,-0.1382330145,0. Na,0,-3.2504064019,0.3433548046,0. Na,0,2.8250981874,1.1323324148,0.

04

C,0,-1.1954310018,-0.1376073235,0. Al,0,-2.3301381502,-1.7327641155,0. Al,0,1.6476535831,1.8418815702,0. Al,0,0.4999663809,-1.2999655508,0. B,0,-0.1573401257,0.8207105245,0. Na,0,3.3881891952,-0.635568401,0. Na,0,-2.4093810017,1.9028242561,0.

05

C,0,0.2048008777,0.713973951,0. Al,0,-1.5319061867,1.5356956088,0. Al,0,2.5568292516,-1.8427667157,0. Al,0,-0.3820154835,-1.2743883531,0. B,0,1.4144960085,-0.0191875337,0. Na,0,-3.3189490727,-0.9764647133,0. Na,0,1.793726725,2.467252286,0.

06

Al,0,0.,0.,-1.309986408 Al,0,0.,-1.9819195414,1.3149199402


Al,0,0.,1.9819195414,1.3149199402 C,0,0.,0.,0.5918942511 B,0,0.,0.,2.0236680844 Na,0,0.,-3.1372504036,-1.399090574 Na,0,0.,3.1372504036,-1.399090574

07 Al,0,0.,0.,-1.8814260198

Al,0,0.,-1.9189636801,1.7260853256 Al,0,0.,1.9189636801,1.7260853256 Na,0,0.,-2.9296315361,-1.1359176144 Na,0,0.,2.9296315361,-1.1359176144 B,0,0.,0.,0.2061196176 C,0,0.,0.,1.6322056397

08 C,0,0.6688491827,-1.4731392006,0.

Al,0,2.5631220345,-1.2153523665,0. Al,0,-2.7402870619,-1.0994152035,0. Al,0,0.0550236834,0.4671121536,0. B,0,-0.7170288501,-1.6095764957,0. Na,0,2.7349339381,1.836849794,0. Na,0,-2.6333407266,1.8805362987,0.

09

C,0,0.9910348972,0.1075948199,0. Al,0,2.8759549535,-0.4249668327,0. Al,0,-2.1682470689,-1.1888504528,0. Al,0,0.4540672659,-1.8947093052,0. B,0,-0.4282429082,0.1965624351,0. Na,0,-2.7945548432,1.6099229378,0. Na,0,0.9929167437,2.4260804579,0.


SI2-Table 4 Mg2+[CBAl3]2― B3LYP/6-311+G(d) ΔE CCSD(T)/6-311+G(2df)//B3LYP/6-311+G(d) ΔE 01 -990.3551597 1.9 -988.3924972 0.0 02 -990.3581933 0.0 -988.3889679 2.2 03 -990.349854 5.2 -988.3881677 2.7 04 -990.3495738 5.4 -988.3816949 6.8 05 -990.3446231 8.5 -988.376762 9.9 06 -990.3396081 11.7 -988.3757267 10.507 -990.3359297 14.0 -988.3713082 13.308 -990.3306183 17.0 -988.3698041 14.2

01

Al,0,2.0506138131,-0.9458660299,0. Al,0,-0.8041791165,-1.6847443872,0. Al,0,1.3605299246,1.8495486219,0. C,0,0.2745825511,-0.0119414555,0. B,0,-0.6838963911,1.0391811969,0. Mg,0,-2.8491615612,0.3472304137,0.

02

C,0,1.165654151,-0.0361909761,0. Al,0,2.8549260523,-1.0258900068,0. Al,0,-1.8807602312,-1.8656892943,0. Al,0,0.5019762208,1.8014130793,0. B,0,-0.1017539242,-0.6348967963,0. Mg,0,-2.2943494387,0.9908319742,0.

03


Al,0,0.4225678703,-1.8716006916,0. Al,0,2.3743589103,0.0419397204,0. Al,0,-1.2717947072,1.9376824226,0. C,0,0.131037683,0.0972191094,0. B,0,0.7353038574,1.3907073295,0. Mg,0,-2.0568987138,-0.6893542603,0.

04

Al,0,2.0524782381,1.0729418515,0. C,0,-1.1234694099,-0.1512110681,0. Al,0,-0.7908924864,1.8225706244,0. Al,0,-2.4720553462,-1.5670507098,0. B,0,0.2727775147,-0.2358689118,0. Mg,0,2.1951770697,-1.7461683661,0.

05 C,0,-0.0236664379,0.8837775881,0.

Al,0,-1.8041916366,1.6236815729,0. Al,0,3.3546801894,-0.0515426806,0. Al,0,0.2487145902,-1.1320382657,0. B,0,1.3651614041,0.8764208264,0. Mg,0,-2.6058845491,-1.1975340412,0.

06 C,0,0.7510561599,0.4858521408,0.

Al,0,0.6636390563,2.4666204894,0. Al,0,-0.1229051592,-1.8564289707,0. Al,0,-2.7686424501,-0.1723356725,0. B,0,-0.6371505872,0.2642019301,0. Mg,0,2.4292403304,-0.8840271771,0.


07 C,0,0.3354489019,0.2361475116,0.

Al,0,2.1508210877,-0.7779171174,0. Al,0,-3.2204068711,0.5896311828,0. Al,0,-0.3159315422,-1.8068443134,0. B,0,-1.0545786402,0.3460936847,0. Mg,0,1.7726120439,1.8997283917,0.

08 C,0,0.8153614527,0.3042124559,0.

Al,0,2.5732002017,-0.5406763602,0. Al,0,-2.7430635468,-0.1619470403,0. Al,0,-0.0678298806,-1.6959458351,0. B,0,-0.6141485071,0.3742623478,0. Mg,0,0.0478656102,2.4587043419,0.


SI3-1 The details of MD simulations. General parameters: Max. points for each Traj. = 3500 and 4000 Total Number of Trajectories = 1 Random Number Generator Seed = 398465 Trajectory Step Size = 0.500 sqrt(amu)*bohr Sampling parameters: Vib Energy Sampling Option = Thermal sampling TS Sampling direction = Forward

Vib Sampling Temperature = 300.0 K and 400.0 K Rot Energy Sampling Option = Thermal distribution (symmetric top) Rot Sampling Temperature = 300.0 K and 400.0 K Start point scaling criteria = 1.000D-05 Hartree Integration parameters: Correction Scheme = Fifth order polynomial fit Project trans/rot in grad. = True Project in prediction step = True Project in correction step = True Integration Scheme = Bulirsch-Stoer method Integration Step Size = 2.000D-01 femtosec Truncation Error Criteria = 1.000D-08 bohr Energy Error Criteria = 1.000D-04 Hartree Hessian evaluation = Full Hessian always

SI3-2 Potential energy of three designed systems [XCAl3]q (X,q)=(B,-2), (C,-1) and

(N,0). (a) [BCAl3]2−, (b) [C2Al3]−, and (c) [NCAl3] along the MD trajectory at

B3LYP/6-31G(d) level, respectively. Born-Oppenheimer molecular dynamics

simulation is performed for 10ps at 300K and 400K. Potential energy (in au) versus

time (in ps).


(a)

300K

0 2 4 6 8 10

-790.130

-790.128

-790.126

-790.124

-790.122

-790.120

-790.118

-790.116

-790.114

PE,H

artre

e

Time,ps

400K

0 2 4 6 8 10-790.132

-790.130

-790.128

-790.126

-790.124

-790.122

-790.120

-790.118

PE,H

artre

e

Time,ps[BCAl3]2-

(b)

0 2 4 6 8 10-803.486

-803.484

-803.482

-803.480

-803.478

-803.476

-803.474

-803.472

-803.470

PE,

Har

tree

Time,ps

300K

0 2 4 6 8 10-803.486

-803.484

-803.482

-803.480

-803.478

-803.476

-803.474

-803.472

-803.470

-803.468

PE,H

artre

e

Time,ps

400K

[C2Al3]-

(c)

300K 400K

0 2 4 6 8 10-820.124

-820.122

-820.120

-820.118

-820.116

-820.114

-820.112

-820.110

-820.108

PE,H

artre

e

Time,ps0 2 4 6 8 10

-820.124

-820.122

-820.120

-820.118

-820.116

-820.114

-820.112

-820.110

-820.108

-820.106

PE

,Har

tree

Time,ps

[NCAl3]


SI4-Table 1 Calculated molecular properties of the [BCAl3]2− (pptC) structures.

BCAl32−, C2v, 1A1 B3LYP/aug-cc-pVTZ MP2/ aug-cc-pVTZ CCSD(T)/ aug-cc-pVTZ

R(C1-B2), Å 1.461 1.485 1.486

R(C1-Al3,4), Å 2.044 2.030 2.035

R(C1-Al5), Å 1.917 1.938 1.939

<Al5C1Al3º 105.0 103.3 103.3

-Etot, au -790.2375416 -788.679885 -788.7317903

ω1(a1), cm-1 1190 1209 1165

ω2(a1), cm-1 544 535 539

ω3(a1), cm-1 325 350 340

ω4(a1), cm-1 158 177 162

ω5(b1), cm-1 210 202 197

ω6(b1), cm-1 122 111 112

ω7(b2), cm-1 656 721 708

ω8(b2), cm-1 528 510 514

ω9(b2), cm-1 79 96 99


SI4-Table 2 Calculated molecular properties of the [C2Al3]− (pptC) structures. C2Al3

−, C2v, 1A1 B3LYP/aug-cc-pVTZ MP2/ aug-cc-pVTZ CCSD(T)/aug-cc-pVTZ

R(C1-C2), Å 1.337 1.3527 1.359

R(C1-Al3,4), Å 2.107 2.0911 2.107

R(C1-Al5), Å 1.925 1.9394 1.935 <Al5C1Al3

º 111.6 110.0 110.7

-Etot, au -803.5806862 -802.0023153 -802.0580572 ω1(a1), cm-1 1453 1454 1408

ω2(a1), cm-1 555 547 560 ω3(a1), cm-1 339 350 349

ω4(a1), cm-1 168 170 174 ω5(b1), cm-1 222 224 216

ω6(b1), cm-1 121 101 105 ω7(b2), cm-1 672 662 666

ω8(b2), cm-1 609 643 649

ω9(b2), cm-1 60 53 60


SI4-Table 3 Calculated molecular properties of the [NCAl3] (pptC) structures. NCAl3, C2v, 1A1 B3LYP/aug-cc-pVTZ MP2/ aug-cc-pVTZ CCSD(T)/ aug-cc-pVTZ

R(C1-N2), Å 1.275 1.293 1.298 R(C1-Al3,4), Å 2.197 2.171 2.192 R(C1-Al5), Å 1.986 1.988 1.976 <Al5C1Al3

º 116.1 114.0 116.3 -Etot, au -820.2221039 -818.6223296 -818.678994

ω1(a1), cm-1 1549 1490 1496 ω2(a1), cm-1 483 493 496 ω3(a1), cm-1 315 319 329 ω4(a1), cm-1 157 163 162 ω5(b1), cm-1 192 199 201 ω6(b1), cm-1 114 107 112 ω7(b2), cm-1 594 581 606 ω8(b2), cm-1 486 563 525 ω9(b2), cm-1 47 42 37

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