Stability of Complexes Formed by Metal Ions (Na+ K+ Ca2+ Mg2+) and Cytosine Isomers

Stability and isomerization of complexes formed by metal ions and cytosine isomers in aqueous phase

Hongqi Ai1*, Jingjing Liu1 andKwaichow Chan2

1Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan, Jinan City, 250022, P. R. China

2Department of Natural Science, Albany State University,Albany, GA 31705, USA

*Author to whom the correspondence should be addressed. E-mail address:

Supporting information

Figure S1.Structures of Cn

Figure S2 Structures and activation energies of isomerization processes of C1C4 and C1M+/2+ C4M+/2+. Data in parentheses don’t include the ZPVE corrections. Values tagged with a and b are from ref [30] calculated at the MPWB1K/aug-cc-pVDZ level under 490K and 1000K conditions, withc and d are from ref [26] obtained at MP2/6-311++G(d,p)//MP2/6-31G(d) level and from [8] obtained at B3LYP/6-311+G(2df,2p) level, respectively.

Table S1.Relative energies (kJ/mol) of CnM+/2+ and Cn in aqueous(Ea) and gas(Eg)phasesat the B3LYP/6-311++G(d,p) level

M+/2+ / Na+ / K+ / Ca2+ / Mg2+ / C
Ea / Eg / Ea / Eg / Ea / Eg / Ea / Eg / Ea / Eg
C1M+/2+ / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 0 / 0
CxM+/2+ / 15.8 / 16.7,20.5d / 14.9 / 17.2 / 14.0 / -1.1,0.4d / 13.2 / -1.8,-0.4d / 16.0 / 27.8
C2MII+/2+
C2MI+/2+ / 30.3a / 74.5a,77.8d / 24.4a / 62.3a / 24.6a / 152.2a,159.8d / 36.5a / 202.8a, 209.6d / 22.3 / 8.7
22.7 / 81.1,83.3 c / 24.1 / 74.2,75.3c / 22.8 / 166.6,167.4b / 16.8 / 179.8,188.3b / - / 9.6c
C3MI+/2+
C3MII+/2+ / 25.4
28.8a / 82.4,87.0d
89.9a / 27.2
36.7a / 76.9
77.7a / 25.6
28.7a / 162.4,173.2d
175.9a / 22.1
40.5a / 172.6,200.4d
224.2a / 25.3 / 15.6
C4MII+/2+
C4MI+/2+ / 39.3a,
50.4 / 55.1a,59.8c,50.6d,
109.2 / 35.6a
44.2 / 50.8a, 54.0c
98.4 / 55.1a,
64.1 / 121.9a,120.9d,130.5b
225.3 / 98.6a
70.1 / 126.7a,133.5d,135.6b
- / 32.1 / 4.4
5.4c
C5MII+/2+ / 35.3a / 37.2a,32.6d, 41.0c / 33.8a / 33.9a, 36.8c / 46.9a / 76.1a,73.6d,83.7b / 51.8a / 81.6a,86.6d,90.4b / 32.7 / 7.8
C5MI+/2+ / 55.7 / 122.2 / - / 112.5 / 101.6 / 204.3 / 100.4 / 186.5 / - / 8.8c
C6MII+/2+ / 82.0a / 111.4a / 84.2a / 109.7a / 77.5 / 148.8a / 143.3 / 151.4a / 85.6 / 78.4
C7MI+/2+ / 82.1 / 125.1,124.7d / 83.6 / 120.9 / 80.5 / 190.9 / 75.0 / 199.6 / 83.6 / 70.6
C8MI+/2+ / 93.6 / 102.8,92.9d / 95.3 / 108.9 / 86.9 / 72.3,65.3d / 73.3 / 50.9, 51.9d / 100.5 / 134.9
C9MII+/2+ / 80.5a / 127.5a,127.6 / 80.7a / 121.9a / 77.4a / 202.8a / 68.9a / 213.6a / 79.5 / 59.0
C10MI+/2+ / 93.4 / 146.7,145.6d / 95.5 / 144.9 / 88.7 / 178.8 / 79.4 / 181.2 / 96.8 / 116.9
C11MI+/2+ / 93.3 / 166.1,165.7d / 94.8 / 161.5 / 92.1 / 236.7 / 119.1 / 245.4 / 94.4 / 106.3
C12MI/II+/2+ / 90.0a / 155.6,146.9d / 92.0a / 148.5 / 92.3a / 232.3 / 81.4a / 246.1 / 90.2 / 91.2
C13MII+/2+
C13MI+/2+ / 84.6a
104.1 / 87.4a,77.0d
252.5 / 86.1a / 93.2a / 78.6a / 82.4a,77.0d / 65.8a / 59.9a,62.3d / 88.5 / 93.0

a means CnMII+/2+ value and others are CnMI+/2+ values. bfrom Ref [29] at the B3LYP/6-311+G(2df,2p)level.c from Ref [8] at the B3LYP/6-311+G(2df,2p) level. d from Ref [24] at the CCSD(T)/cc-pvtzlevel.

Table S2 Relative energies (kJ/mol) of CnNaI/II+ and CnCaI/II2+ obtained under various models and radii

model / PCM / CPCM
radius / UA0 / UAHF / UFF / PAULING / BONDI / KLAMT / UA0
C1Na+ / 0 / 0 / 0 / 0 / 0 / 0 / 0
C2NaI+ / 22.7 / 35.7 / 28.6 / 31.2 / 46.4 / 35.6 / 22.3
C3NaI+ / 25.4 / 37.5 / 32.8 / 34.5 / 47.2 / 39.2 / 25.2
C4NaII+ / 39.3 / 40.7 / 44.9 / 53.8 / 57.0 / 49.0 / 42.2
C1Ca2+ / 0 / 0 / 0 / 0 / 0 / 0 / 0
C2CaII2+ / 24.6 / 55.1 / 29.8 / 33.7 / 50.1 / 74.5 / 25.8
C3CaI2+ / 25.6 / 57.0 / 32.1 / 34.0 / 63.0 / 76.4 / 26.1
C4CaII2+ / 55.1 / 63.9 / 61.5 / 67.0 / 64.6 / 79.3 / 58.9

Table S3. Dipole moments (debye) of Cn and CnMI/II+/2+ in gas phase obtained at the B3LYP/6-311++G(d,p) level

M+/2+ / Na+ / K+ / Ca2+ / Mg2+ / Cng / Cnl
C1M+/2+ / 4.3 / 4.6 / 9.2 / 7.9 / 6.8,6.9b,6.3a / 10.4,9.3b
CxM+/2+ / 1.7 / 2.1 / 7.4 / 6.1 / 8.6,8.4b,--- / 13.3,12.0b
C2MI+/2+ / 10.7 / 11.0 / 19.0 / 18.4 / 5.0,5.0b,4.6a / 7.0,6.5b
C2MII+/2+ / 11.3 / 11.1 / 19.7 / 17.2
C3MI+/2+ / 12.9 / 13.2 / 21.3 / 20.6 / 2.5, ---, 2.4a / 3.7
C3MII+/2+ / 13.7 / 13.6 / 22.2 / 19.2
C4MI+/2+ / 10.4 / 10.9 / 16.9 / - / 3.4,3.5b,3.3a / 4.9,4.8b
C4MII+/2+ / 7.6 / 8.2 / 13.1 / 11.9
C5MI+/2+ / 10.5 / 10.9 / 11.5 / 10.4 / 4.8,---, 4.5a / 7.1
C5MII+/2+ / 5.5 / 6.0 / 15.8 / 14.7
C13MI+/2+ / 12.4 / 15.9 / 5.7 / 8.9
C13MII+/2+ / 4.2 / 8.3

a from Ref [14] at theRIMP2/TZVPP-auxTZVPP level.b from Ref [22] at the B3LYP/6-31++G(d,p) level.