H C N

H C N

H C N

Supporting information

Crystal structure of ZIFs were taken from Crystallography Open Database. ZIF-7

(Zn- (bim)2) is formed by bridging benzimidazolate (bim) anions and zinc cations

with soladite (SOD) topology. Schemes S1-S3 show the structures of ZIFs in a

2×2×2 unit cell. Table S1 also shows structural characteristics of ZIFs [1, 2].

Scheme S1. Unit cell (2×2×2) of ZIF-7 (Zn:Green, N:Blue, C:Gray, H:White) (hexagonal

withcell lengths (Å): a = b = 22.989, c = 15.763[1]).

H C N

H C N

H C N

Scheme S2. Unit cell (2×2×2) of ZIF-8 (Zn:Green, N:Blue, C:Gray, H:White) (cubic with cell

lengths (Å): a = b =c= 16.991 [1]).

Scheme S3. Unit cell (2×2×2) of ZIF-9 (Zn:Green, N:Blue, C:Gray, H:White) (hexagonal with

cell lengths (Å): a = b = 22.944, c = 15.747 [1]).

H C N

H C N

H C N

Table S1. Structural characteristics of ZIFs [1, 2].property ZIF-7 ZIF-8 ZIF-9

Pore characterization Largest Cavity Diameter (Å) quantities. Pore Limiting Diameter (Å)

5.6

2.4

11.4

3.4

5.6

2.4

Accessible volume Volume (cm3/g)

and surface area Surface Area (m2/g)

0.078

516

0.485

1531

0.076

497

Scheme S4. Structure and atom labeling of 5-Fluorouracil (5-FU).

Table S2. Lennard-Jones parameters for 5-FU [3].atom (A°) /

N 3.250 85.578 C 3.340 43.292 O 3.340 105.714

H-N 1.069 7.903 H-A 2.511 7.551

F 3.118 30.707 *H_N denotes the hydrogen atom bonding to nitrogen atom, H_A is the hydrogen atoms bonding to carbon atom of the ring.

chargeatom

123456789101112

C C C C H F O NH NH O

0.1647730.2811050.1268030.0510390.187502-0.335558-0.461112-0.1323240.389726-0.2337470.415200-0.453408

H C N

H C N

H C N

Table S3. Atomic charges of 5-FU calculated by DFT/B3LYP/6-311++G(d,p).

Scheme S5. Structure and atom labeling ofHydroxiurea.

Table S4. Lennard-Jones parameters for Hydroxiurea.atom (A°) ϵ (kcal/mol) H-N 0.000 0.000

N(NH2) 3.250 0.170 O-H 3.120 0.170

H C N

H C N

H C N C 3.750 0.105

O=c 2.960 0.210 H-O 0.000 0.000

Table S5. Atomic charges of Hydroxiurea calculated by DFT/B3LYP/6-311++G(d,p).

atom charge

1 C 0.2833482 O -0.5776403 N -0.4795964 H 0.3448965 H 0.3237726 N -0.3043967 H 0.3476718 O -0.3301969 H 0.392141

Scheme S6. Structure and atom labeling ofMercaptopurine.

Table S6. Lennard-Jones parameters for Mercaptopurine.atom (A°) ϵ (kcal/mol)

S 3.560 0.1698 N 3.250 0.170 O 2.960 0.210

H C N

H C N

H C N C 3.550 0.070

H-C 2.420 0.030 H-N 0.000 0.000

Table S7. Atomic charges of Mercaptopurine calculated by DFT/B3LYP/6-311++G(d,p).

atom charge

1 C -0.0614512 C 0.1450073 C -0.2738614 C 0.0177715 C 0.1773186 N -0.2613567 N -0.0670708 S -0.0500369 N -0.33728710 H 0.35575311 N -0.36820112 H 0.36194913 H 0.13699514 H 0.224468

Table S8. Atomic charges of ZIF-7estimated using REPEAT method [4].

number atom charge number atom charge number atom charge1 C -0/131 35 C -0/2013 69 H 0/1432 C -0/137 36 C -0/1716 70 H 0/14823 C -0/1266 37 Zn 0/3725 71 H 0/14634 C -0/1309 38 Zn 0/3561 72 H 0/14295 C -0/137 39 Zn 0/379 73 H 0/10816 C -0/1265 40 Zn 0/3726 74 H 0/11057 C -0/0755 41 Zn 0/3561 75 H 0/10228 C 0/0921 42 Zn 0/3789 76 H 0/10849 C -0/0571 43 N -0/1244 77 H 0/110810 C -0/0766 44 N -0/1069 78 H 0/102711 C -0/0933 45 N -0/1275 79 H 0/1454

H C N

H C N

H C N

12 C -0/0589 46 N -0/124 80 H 0/157 13 C -0/1925 47 N -0/1062 81 H 0/149 14 C -0/2334 48 N -0/1266 82 H 0/145 15 C -0/2113 49 N -0/0486 83 H 0/15716 C -0/1913 50 N -0/0249 84 H 0/148817 C -0/2316 51 N -0/0439 85 H 0/131518 C -0/2101 52 N -0/049 86 H 0/135319 C -0/1844 53 N -0/0252 87 H 0/127720 C -0/1857 54 N -0/0445 88 H 0/131721 C -0/1647 55 N -0/0826 89 H 0/135522 C -0/185 56 N -0/0672 90 H 0/127923 C -0/1865 57 N -0/0779 91 H 0/139924 C -0/1654 58 N -0/0833 92 H 0/141425 C -0/1859 59 N -0/0681 93 H 0/148226 C -0/2016 60 N -0/0784 94 H 0/139827 C -0/2237 61 N 0/011 95 H 0/141328 C -0/1858 62 N 0/0211 96 H 0/148129 C -0/2015 63 N 0/0012 97 H 0/148730 C -0/2236 64 N 0/0112 98 H 0/159631 C -0/1541 65 N 0/0214 99 H 0/1508

32 C -0/2012 66 N 0/0015 100 H 0/149 33 C -0/1717 67 H 0/1482 101 H 0/156 34 C -0/154 68 H 0/1463 102 H 0/1508

Table S9. Atomic charges of ZIF-8estimated using REPEAT method.

number atom charge number atom charge number atom Charge 1 C -0/1927 35 C 0/13 69 H 0/141 2 C -0/141 36 C -0/0466 70 H 0/1727 3 C -0/189 37 Zn 0/4184 71 H 0/1513 4 C -0/2522 38 Zn 0/4194 72 H 0/1596 5 C -0/1813 39 Zn 0/4251 73 H 0/185 6 C -0/2164 40 Zn 0/4172 74 H 0/1471 7 C -0/2359 41 Zn 0/4273 75 H 0/1418 8 C -0/1591 42 Zn 0/4199 76 H 0/1635 9 C -0/1272 43 N -0/0653 77 H 0/1615

10 C -0/2229 44 N -0/1827 78 H 0/1325 11 C -0/221 45 N -0/098 79 H 0/136 12 C -0/1489 46 N -0/1048 80 H 0/1488 13 C -/1403 47 N -0/1336 81 H 0/1724 14 C -0/1935 48 N -0/109 82 H 0/1399 15 C -0/2504 49 N -0/0652 83 H 0/1859 16 C -0/1877 50 N -0/1555 84 H 0/1474 17 C -0/239 51 N -0/182 85 H 0/1501 18 C -0/1618 52 N -0/0607 86 H 0/1607 19 C -0/1768 53 N -0/1355 87 H 0/1327

H C N

H C N

H C N

20 C 0/2189 54 N -0/1163 88 H 0/1623 21 C -0/149 55 N -0/1856 89 H 0/1651 22 C -0/2236 56 N -0/0629 90 H 0/1422 23 C -0/2246 57 N -0/1066 91 H 0/0913 24 C -0/1268 58 N -0/0974 92 H 0/0398 25 C -0/0561 59 N -0/0657 93 H 0/0911 26 C -0/1271 60 N -0/1539 94 H 0/0479 27 C -0/0456 61 N -0/1364 95 H 0/0633 28 C 0/0911 62 N -0/1097 96 H 0/0577 29 C 0/0338 63 N -0/1164 97 H 0/0785 30 C 0/0652 64 N -0/1319 98 H 0/0577 31 C -0/0158 65 N -0/0613 99 H 0/0464 32 C 0/0675 66 N -0/1783 100 H 0/0929 33 C 0/0956 67 H 0/1483 101 H 0/0391 34 C 0/0606 68 H 0/1366 102 H 0/0917

Table S10. Atomic charges of ZIF-9 estimated using REPEAT method. Number atom charge number atom charge number atom charge

12345678910111213141516171819202122

C C C C C C C C C C C C C C C C C C H H H H

-0.1997-0.2019-0.2007-0.2094-0.2036-0.2069-0.1936-0.1902-0.1966-0.2001-0.2013-0.2017-0.2094-0.2072-0.2036-0.1942-0.1964-0.1928-0.1537-0.1477-0.1861-0.1262

103104105106107108109110111112113114115116117118119120121122123124

H H H H H H C C C C C C C C C C C C C C C C

-0.2467-0.2455-0.2477-0.2159-0.2217-0.2210-0.1170-0.1094-0.1144-0.0865-0.0841-0.0907-0.1029-0.1062-0.0992-0.1152-0.1143-0.1097-0.0863-0.0904-0.0837-0.1028

205206207208209210211212213214215216217218219220221222223224225226

H H H H H H H H H H H H Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn

0.17130.17220.17260.17200.17370.17310.17080.17020.16990.17150.17270.17300.11110.11320.11270.12890.12850.12630.11660.11640.11800.1115

H C N

H C N

H C N

23242526272829303132333435363738394041424344454647484950515253545556575859606162

H H H H H H H H H H H H H H C C C C C C C C C C C C C C C C C C H H H H H H H H

-0.1267-0.1197-0.1690-0.1845-0.1835-0.1644-0.7680-0.1336-0.1265-0.1202-0.1267-0.1720-0.1542-0.1190-0.2512-0.2490-0.2423-0.2507-0.2450-0.2516-0.1836-0.1696-0.1858-0.2491-0.2415-0.2486-0.2507-0.2505-0.2447-0.1840-0.1859-0.1700-0.2255-0.2293-0.2263-0.2107-0.2124-0.2126-0.1879-0.1889

125126127128129130131132133134135136137138139140141142143144145146147148149150151152153154155156157158159160161162163164

C C H H H H H H H H H H H H H H H H H H C C C C C C C C C C C C C C C C C C H H

-0.0992-0.1062-0.0129-0.0071-0.0186-0.00020.0009-0.0007-0.0602-0.0667-0.0504-0.0122-0.0192-0.0073-0.0001-0.00110.0011-0.0600-0.0506-0.0663-0.00410.01430.01130.01330.01580.01210.02440.03250.0327-0.00380.01130.01390.01360.01240.01740.02480.03340.0325-0.0776-0.0637

227228229230231232233234235236237238239240241242243244245246247248249250251252253254255256257258259260261262263264265266

Zn Zn Zn Zn Zn Zn Zn Zn N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N

0.11270.11320.12890.12640.12850.11680.11800.11650.15380.15250.15100.14690.14540.14790.13200.12820.13060.15300.15050.15240.14680.14750.14520.13220.13080.12830.17310.17360.17310.17310.17390.17350.16770.16770.17030.17350.17310.17360.17310.1735

H C N

H C N

H C N

63646566676869707172737475767778798081828384858687888990919293949596979899100101102

H H H H H H H H H H C C C C C C C C C C C C C C C C C C H H H H H H H H H H H H

-0.1974-0.2267-0.2261-0.2292-0.2109-0.2126-0.2127-0.1881-0.1972-0.1881-0.2443-0.2513-0.2463-0.1994-0.1999-0.1980-0.2355-0.2361-0.2349-0.2430-0.2463-0.2512-0.1993-0.1978-0.2010-0.2359-0.2352-0.2366-0.2455-0.2515-0.2475-0.2466-0.2477-0.2456-0.2162-0.2216-0.2222-0.2478-0.2472-0.2513

165166167168169170171172173174175176177178179180181182183184185186187188189190191192193194195196197198199200201202203204

H H H H H H H H H H H H H H H H C C C C C C C C C C C C C C C C C C H H H H H H

-0.0735-0.0597-0.0567-0.0630-0.0738-0.0663-0.0597-0.0733-0.0735-0.0642-0.0597-0.0629-0.0565-0.0740-0.0599-0.06630.45830.43840.45160.43110.42460.43500.45100.44850.43550.45390.45170.43870.43100.43500.42400.45100.43550.44860.17180.17320.17340.17090.17000.1701

267268269270271272273274275276277278279280281282283284285286287288289290291292293294295296297298299300301302303304305306

N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N

0.17390.16780.17020.16750.16510.16580.16570.15170.15160.15090.16180.16070.16070.16470.16570.16580.15160.15080.15170.16190.16070.16080.16650.16890.16770.16840.16820.16760.16010.16120.16200.16700.16770.16880.16840.16760.16830.16000.16170.1610

H C N

H C N

H C N

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