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 and Kwaichow 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: [email protected]

Supporting information

Figure S1. Structures of Cn +/2+ +/2+. Figure S2 Structures and activation energies of isomerization processes of C1 C4 and C1M  C4M 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, with c 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.

+/2+ Table S1. Relative energies (kJ/mol) of CnM and Cn in aqueous (Ea) and gas(Eg) phases at 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

+/2+ C1M 0 0 0 0 0 0 0 0 0 0

+/2+ d d d CxM 15.8 16.7,20.5 14.9 17.2 14.0 -1.1,0.4 13.2 -1.8,-0.4 16.0 27.8

+/2+ a a d a a a a d a a d C2MII 30.3 74.5 ,77.8 24.4 62.3 24.6 152.2 ,159.8 36.5 202.8 , 209.6 22.3 8.7

+/2+ c c b b c C2MI 22.7 81.1,83.3 24.1 74.2,75.3 22.8 166.6,167.4 16.8 179.8,188.3 - 9.6

+/2+ d d d C3MI 25.4 82.4,87.0 27.2 76.9 25.6 162.4,173.2 22.1 172.6,200.4 25.3 15.6

+/2+ a a a a a a a a C3MII 28.8 89.9 36.7 77.7 28.7 175.9 40.5 224.2

+/2+ a, a c d a a c a a d b a a d b C4MII 39.3 55.1 ,59.8 ,50.6 , 35.6 50.8 , 54.0 55.1 , 121.9 ,120.9 ,130.5 98.6 126.7 ,133.5 ,135.6 32.1 4.4

+/2+ c C4MI 50.4 109.2 44.2 98.4 64.1 225.3 70.1 - 5.4

+/2+ a a d c a a c a a d b a a d b C5MII 35.3 37.2 ,32.6 , 41.0 33.8 33.9 , 36.8 46.9 76.1 ,73.6 ,83.7 51.8 81.6 ,86.6 ,90.4 32.7 7.8

+/2+ c C5MI 55.7 122.2 - 112.5 101.6 204.3 100.4 186.5 - 8.8

+/2+ a a a a a a C6MII 82.0 111.4 84.2 109.7 77.5 148.8 143.3 151.4 85.6 78.4

+/2+ d C7MI 82.1 125.1,124.7 83.6 120.9 80.5 190.9 75.0 199.6 83.6 70.6

+/2+ d d d C8MI 93.6 102.8,92.9 95.3 108.9 86.9 72.3,65.3 73.3 50.9, 51.9 100.5 134.9

+/2+ a a a a a a a a C9MII 80.5 127.5 ,127.6 80.7 121.9 77.4 202.8 68.9 213.6 79.5 59.0

+/2+ d C10MI 93.4 146.7,145.6 95.5 144.9 88.7 178.8 79.4 181.2 96.8 116.9

+/2+ d C11MI 93.3 166.1,165.7 94.8 161.5 92.1 236.7 119.1 245.4 94.4 106.3

+/2+ a d a a a C12MI/II 90.0 155.6,146.9 92.0 148.5 92.3 232.3 81.4 246.1 90.2 91.2

+/2+ a a d a a a a d a a d C13MII 84.6 87.4 ,77.0 86.1 93.2 78.6 82.4 ,77.0 65.8 59.9 ,62.3 88.5 93.0

+/2+ C13MI 104.1 252.5 a +/2+ +/2+ b c d means CnMII value and others are CnMI values. from Ref [29] at the B3LYP/6-311+G(2df,2p) level. from Ref [8] at the B3LYP/6-311+G(2df,2p) level. from Ref [24] at the CCSD(T)/cc-pvtz level.

+ 2+ Table S2 Relative energies (kJ/mol) of CnNaI/II and CnCaI/II 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

2+ C1Ca 0 0 0 0 0 0 0 2+ C2CaII 24.6 55.1 29.8 33.7 50.1 74.5 25.8 2+ C3CaI 25.6 57.0 32.1 34.0 63.0 76.4 26.1 2+ C4CaII 55.1 63.9 61.5 67.0 64.6 79.3 58.9 +/2+ Table S3. Dipole moments (debye) of Cn and CnMI/II in gas phase obtained at the B3LYP/6- 311++G(d,p) level +/2+ + + 2+ 2+ M Na K Ca Mg Cng Cnl +/2+ b a b C1M 4.3 4.6 9.2 7.9 6.8,6.9 ,6.3 10.4,9.3 +/2+ b b CxM 1.7 2.1 7.4 6.1 8.6,8.4 ,--- 13.3,12.0 +/2+ b a b C2MI 10.7 11.0 19.0 18.4 5.0,5.0 ,4.6 7.0,6.5 +/2+ C2MII 11.3 11.1 19.7 17.2 +/2+ a C3MI 12.9 13.2 21.3 20.6 2.5, ---, 2.4 3.7 +/2+ C3MII 13.7 13.6 22.2 19.2 +/2+ b a b C4MI 10.4 10.9 16.9 - 3.4,3.5 ,3.3 4.9,4.8 +/2+ C4MII 7.6 8.2 13.1 11.9 +/2+ a C5MI 10.5 10.9 11.5 10.4 4.8,---, 4.5 7.1 +/2+ C5MII 5.5 6.0 15.8 14.7 +/2+ C13MI 12.4 15.9 5.7 8.9 +/2+ C13MII 4.2 8.3 a from Ref [14] at the RIMP2/TZVPP-auxTZVPP level. b from Ref [22] at the B3LYP/6-31++G(d,p) level.