supplementary materials for -...
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www.sciencemag.org/content/341/6149/1230444/suppl/DC1
Supplementary Materials for
The Chemistry and Applications of Metal-Organic Frameworks
Hiroyasu Furukawa, Kyle E. Cordova, Michael O’Keeffe, Omar M. Yaghi*
*Corresponding author. E-mail: [email protected]
Published 30 August 2013, Science 341, 1230444 (2013)
DOI: 10.1126/science.1230444
This PDF file includes:
Materials and Methods
Figs. S1 to S8
Tables S1 to S5
References (135–363)
Related web sites
Other supplementary material for this manuscript includes the following:
CSD reference codes for MOFs
Fig. S1. The great number and diversity of inorganic SBUs (A) and organic linkers (B) used to
create metal-organic frameworks referred to in the text by abbreviations. C, black; O, red; N,
green; S, yellow; P, purple, Cl, light green; metal ions, blue polyhedra. Hydrogen atoms are
omitted for clarity.
Table S1: Structure of inorganic and organic SBUs used to form MOFs.
Zn4O(BDC)3
MOF-5, IRMOF-1
Zn4O(BDC-NH2)3
IRMOF-3
Zn4O(fumarate)3
Zn4O(TPDC)3
IRMOF-16
Zn4O(BTB)2
MOF-177
Zn4O(BTE)2
MOF-180
Zn4O(BBC)2
MOF-200
(Zn4O)3(BTE)4(BPDC)3
MOF-210
(Zn4O)3(BTB)4(BDC-NH2)3
UMCM-1-NH2
Zn4O(BPP34C10DA)3
MOF-1001
Zn4O[(BDC)0.72(BDC-NH2)0.10(BDC-Br)0.39(BDC-NO2)0.20(BDC-(Me)2)0.47-
(NDC)0.39(BATA)0.34(BPEBDC)0.39]
MTV-MOF-5
Cu3(BTC)2
HKUST-1, MOF-199
Cu3(TATB)2
PCN-6′
Cu3(TATAB)2
Meso-MOF-1
Cu3(TTCA)2
PCN-20
Cu3(HTB)2
PCN-HTB′
Cu3(BBC)2
MOF-399
Zn3(TPBTM)
Cu3(BTPI)
NOTT-112
Cu3(PTEI)
NOTT-116, PCN-68
Cu3(BTEI)
PCN-61
Cu3(NTEI)
PCN-66
Cu3(BTTI)
PCN-69, NOTT-119
Cu3(TTEI)
PCN-610, NU-100
Cu3(TPBTM)
Cu3(TDPAT)
Cu3(BTETCA)
NU-108
Cu3(BNETPI)
NU-109
Cu3(BHEHPI)
NU-110
Cu3(BHEI)
NU-111
M3(BTC)2
M = Zn, Fe, Mo, Cr, and Ru
Cu2(ATC)
MOF-11
Cu2(ADIP)
PCN-14
Zn2(DOT)
MOF-74
M2(DOT)
M = Co, Ni, Mn,
Fe, and Cu
Mg2(DOT)
IRMOF-74-I
Mg2(DH2PhDC)
IRMOF-74-II
Mg2(DH3PhDC)
IRMOF-74-III
Mg2(DH4PhDC)
IRMOF-74-IV
Mg2(DH5PhDC)
IRMOF-74-V
Zn2(DH6PhDC)
IRMOF-74-VI
Mg2(DH7PhDC)
IRMOF-74-VII
Mg2(DH7PhDC-oeg)
IRMOF-74-VII-oeg
Mg2(DH9PhDC)
IRMOF-74-IX
Mg2(DH11PhDC)
IRMOF-74-XI
Zn(MIm)2
ZIF-8
Zr6O4(OH)4(BDC)6
UiO-66
Zr6O4(OH)4(BDC-NO2)6
UiO-66-NO2
Zr6O4(OH)4(BDC-Br)6
UiO-66-Br
Zr6O4(OH)4(BDC-NH2)6
UiO-66-NH2
Zr6O4(OH)4(TpCPP-H2)3
MOF-525
Zr6O8(TpCPP-H2)3
MOF-545
Ni3(BTP)2
Zn3(μ3-O)(D-PTT)6
POST-1
CdCl2(DCDPBN)
Cd(BPy)2(NO3)2
Cr3X(H2O)2O(BDC)3; X = F, OH
MIL-101
Mn3[(Mn4Cl)3(BTT)8]2
Mn-BTT
VO[BDC-(Me)2]
MOF-48
Mn2(TpCPP)2Mn3
PIZA-3
In(ImDC)2
rho-ZMOF
Zr6O4(OH)4[Ir(DPBPyDC)(PPy)2·X]6
Zn3(BDC)3[Cu(Pyen)]
CuSiF6(BPy)2
Zn(BDC)
MOF-2
H3[(Cu4Cl)3(BTTri)8(mmen)12]
CuBTTri
Cu2(PZDC)2(Pyz)
Zn2(BDC)2(BPy)
MOF-508
Cu(DTOA)
Fe(OH)(BDC)
MIL-53
Fe(OH)[BDC-(COOH)2]
MIL-53-(COOH)2
La(H5DTP)(H2O)3
PCMOF-5
Na3(THBTS)
PCMOF-2
Fe(oxalate)(H2O)2
Al(OH)(NDC)
[M6O2(ADB)3(H2O)6](H2O)6(NO3)2, M (III) =
In and Ga, soc-MOF-1
Zn2(NDC)2(DABCO)/Cu2(NDC)2(DABCO)
Zn(Gly-Ala)2
Zn26O3(OH)4(FDA)30·(H2O)12(Et2NH2)6
CPM-7
Co9(OH)2(acetate)(BTC)4(IN)8·(H2O)4(Me2NH2)5]
CPM-24
Ag6(OH)2(H2O)4(TIPA)5
Zn2(TTFTB)
Zn2(oxalate)3
Zn3(HCOO)6
Mn(BDC)
MOF-73
Table S2. CSD refcodes for MOFs referred to in this review (n.a. – not available). CCDC CIF depository request form is available
free of charge via the Internet at http://www.ccdc.cam.ac.uk/Community/Requestastructure/Pages/DataRequest.aspx. WebCSD can be
available via the Internet at http://webcsd.ccdc.cam.ac.uk/index.php.
Material Chemical formula Metal ion Refcode CCDC or DOI Ref.
MOF-5 Zn4O(BDC)3 Zn SAHYIK 256965 13
IRMOF-1 Zn4O(BDC)3 Zn EDUSIF 175572 5
IRMOF-3 Zn4O(BDC-NH2)3 Zn EDUSUR 175574 5
n.a. Zn4O(fumarate)3 Zn XOZXOA 715031 34
IRMOF-16 Zn4O(TPDC)3 Zn EDUWAB 175585 5
MOF-177 Zn4O(BTB)2 Zn ERIRIG 230642 15
MOF-180 Zn4O(BTE)2 Zn CUSXIY 775690 17
MOF-200 Zn4O(BBC)2 Zn CUSXOE 775691 17
MOF-210 (Zn4O)3(BTE)4(BPDC)3 Zn CUSYAR 775693 17
UMCM-1-NH2 (Zn4O)3(BTB)4(BDC-NH2)3 Zn HOMXIR 718531 135
MOF-1001 Zn4O(BPP34C10DA)3 Zn UHUPOD 728415 125
HKUST-1, MOF-199 Cu3(BTC)2 Cu FIQCEN 112954 35
PCN-6′ Cu3(TATB)2 Cu NIBHOW 643188 38
Meso-MOF-1 Cu3(TATAB)2 Cu HEXVEM 638722 36
PCN-20 Cu3(TTCA)2 Cu LUKLIN 685824 39
PCN-HTB′ Cu3(HTB)2 Cu NIBJAK 643190 38
MOF-399 Cu3(BBC)2 Cu BAZGAM 780452 21
n.a. Zn3(TPBTM) Zn SIZPUN 665862 40
NOTT-112 Cu3(BTPI) Cu FOPFAS 706575 41
Material Chemical formula Metal ion Refcode CCDC or DOI Ref.
PCN-68 Cu3(PTEI) Cu HABRAF 764973 43
NOTT-116 Cu3(PTEI) Cu LURRIA 781052 44
PCN-61 Cu3(BTEI) Cu VUJBIM 745528 42
PCN-66 Cu3(NTEI) Cu VUJBOS 745529 42
PCN-69 Cu3(BTTI) Cu QAQNED 806144 45
NOTT-119 Cu3(BTTI) Cu IYOXUQ 828163 136
PCN-610 Cu3(TTEI) Cu HABQUY 764972 43
NU-100 Cu3(TTEI) Cu GAGZEV 777421 24
n.a. Cu3(TPBTM) Cu UXISAW 787640 46
n.a. Cu3(TDPAT) Cu XALXUF 846266 137
n.a. Cu3(TDPAT) Cu XALXUF01 831219 47
NU-108 Cu3(BTETCA) Cu DAWMUL 878099 48
NU-109 Cu3(BNETPI) Cu n.a. DOI: 10.1021/ja3055639 20
NU-110 Cu3(BHEHPI) Cu n.a. DOI: 10.1021/ja3055639 20
NU-111 Cu3(BHEI) Cu n.a. DOI: 10.1021/ja302623w 19
n.a. Zn3(BTC)2 Zn EBUCOT 156777 49
n.a. Fe3(BTC)2 Fe NINVAI 665195 50
TUDMOF-1 Mo3(BTC)2 Mo n.a. n.a. 51
n.a. Cr3(BTC)2 Cr n.a. n.a. 52
n.a. Ru3(BTC)2 Ru IVESOS 814515 53
MOF-11 Cu2(ATC) Cu BIMDEF n.a. 30
PCN-14 Cu2(ADIP) Cu XITYOP 678724 25
Material Chemical formula Metal ion Refcode CCDC or DOI Ref.
MOF-74 Zn2(DOT) Zn FIJDOS 265095 54
CPO-27-Co, Co-MOF-
74 Co2(DOT) Co NAVJAW 270292 138
CPO-27-Co, Co-MOF-
74 Co2(DOT) Co SATNOR 270293 138
CPO-27-Ni, Ni-MOF-74 Ni2(DOT) Ni LECQEQ 288477 139
CPO-27-Ni, Ni-MOF-74 Ni2(DOT) Ni LEJRIC 288478 139
Mn-MOF-74 Mn2(DOT) Mn n.a. n.a. 55
Fe-MOF-74 Fe2(DOT) Fe CAXVII 853659 140
Cu-MOF-74 Cu2(DOT) Cu n.a. n.a. 141
CPO-27-Mg, Mg-MOF-
74, IRMOF-74-I Mg2(DOT) Mg VOGTIV 668974 142
IRMOF-74-II Mg2(DH2PhDC) Mg RAVVUH 841642 22
IRMOF-74-III Mg2(DH3PhDC) Mg RAVWAO 841643 22
IRMOF-74-IV Mg2(DH4PhDC) Mg RAVWES 841644 22
IRMOF-74-V Mg2(DH5PhDC) Mg RAVWIW 841645 22
IRMOF-74-VI Zn2(DH6PhDC) Mg RAVWUI 841647 22
IRMOF-74-VII Mg2(DH7PhDC) Mg RAVXAP 841648 22
IRMOF-74-VII-oeg Mg2(DH7PhDC-oeg) Mg RAVXET 841649 22
IRMOF-74-IX Mg2(DH9PhDC) Mg RAVXIX 841650 22
IRMOF-74-XI Mg2(DH11PhDC) Mg RAVXOD 841651 22
ZIF-8 Zn(MIm)2 Zn VELVOY 602542 56
UiO-66 Zr6O4(OH)4(BDC)6 Zr RUBTAK 733458 57
UiO-66-NO2 Zr6O4(OH)4(BDC-NO2)6 Zr n.a. n.a. 58
Material Chemical formula Metal ion Refcode CCDC or DOI Ref.
UiO-66-Br Zr6O4(OH)4(BDC-Br)6 Zr n.a. n.a. 58
UiO-66-NH2 Zr6O4(OH)4(BDC-NH2)6 Zr n.a. n.a. 58
MOF-525 Zr6O4(OH)4(TpCPP-H2)3 Zr n.a. DOI: 10.1021/ic300825s 59
MOF-545 Zr6O8(TpCPP-H2)3 Zr n.a. DOI: 10.1021/ic300825s 59
n.a. Ni3(BTP)2 Ni UTEWOG 804989 60
POST-1 Zn3(μ3-O)(D-PTT)6 Zn UHOPUC 212735 31
n.a. CdCl2(DCDPBN) Cd DARSEV 261744 67
n.a. Cd(BPy)2(NO3)2 Cd YECFAN n.a. 29
MIL-101 Cr3X(H2O)2O(BDC)3; X = F, OH Cr OCUNAC 605510 143
Mn-BTT Mn3[(Mn4Cl)3(BTT)8]2 Mn JEWYAM 604558 144
MOF-48 VO[BDC-(Me)2] V n.a. DOI: 10.1021/ic201396m 73
PIZA-3 Mn2(TpCPP)2Mn3 Mn n.a. n.a. 76
rho-ZMOF In(ImDC)2 In TEFWIL 294663 145
n.a. Zr6O4(OH)4[Ir(DPBPyDC)(PPy)2·X]6 Zr n.a. DOI: 10.1021/ja300539p 83
n.a. Zn3(BDC)3[Cu(Pyen)] Zn COJGEO 701519 88
n.a. CuSiF6(BPy)2 Cu GORWUF 142080 93
MOF-2 Zn(BDC) Zn GECXUH n.a. 12
CuBTTri H3[(Cu4Cl)3(BTTri)8(mmen)12] Cu n.a. n.a. 98
n.a. Cu2(PZDC)2(Pyz) Cu FEVNOK 249301 146
MOF-508 Zn2(BDC)2(BPy) Zn ECIWUJ 265851 102
n.a. Cu(DTOA) Cu n.a. n.a. 105
MIL-53 Fe(OH)(BDC) Fe POJTOY 690314 147
Material Chemical formula Metal ion Refcode CCDC or DOI Ref.
MIL-53 Fe(OH)(BDC) Fe POJTUE 690316 147
MIL-53-(COOH)2 Fe(OH)[BDC-(COOH)2] Fe n.a. n.a. 106
PCMOF-5 La(H5DTP)(H2O)3 La n.a. DOI: 10.1021/ja310435e 107
PCMOF-2 Na3(THBTS) Na GUXVUR 746416 110
n.a. Fe(oxalate)(H2O)2 Fe n.a. DOI: 10.1007/s00269-
008-0241-7
148
n.a. Al(OH)(NDC) Al WOJJOV 710000 149
soc-MOF-1 [In6O2(ADB)3(H2O)6](H2O)6(NO3)2 In RIDCEN 624028 150
soc-MOF-1 [Ga6O2(ADB)3(H2O)6](H2O)6(NO3)2 Ga n.a. n.a. 119
n.a. Zn2(NDC)2(DABCO) Zn DOWBOH 704442 130
n.a. Cu2(NDC)2(DABCO) Cu DOWBIB 260861 130
n.a. Zn(Gly-Ala)2 Zn BUWLEL 764869 132
CPM-7 Zn26O3(OH)4(FDA)30·(H2O)12(Et2NH2)6 Zn n.a. 867864 134
CPM-24 Co9(OH)2(acetate)(BTC)4(IN)8·(H2O)4(Me2NH2)5] Co IYATAE 824096 133
n.a. Ag6(OH)2(H2O)4(TIPA)5 Ag OYEYOH 845627 23
n.a. Zn2(oxalate)3 Zn VUKXUV 733240 26
n.a. Zn2(TTFTB) Zn n.a. DOI: 10.1021/ja3059827 27
n.a. Zn3(HCOO)6 Zn FIQZAH 238107 151
MOF-73 Mn(BDC) Mn FIJDIM 265094 54
Fig. S2. The isoreticular (maintaining same topology) expansion of archetypical MOFs resulting
from discrete inorganic SBUs combined with ditopic organic linkers to obtain MOFs in a pcu net.
The scaled comparison of the smallest, medium, and largest crystalline structures of MOFs
representative of these nets are shown. The large yellow sphere represents the largest sphere that
would occupy the cavity. Numbers above each arrow represent the degree of volume expansion
from the smallest framework. Atom colors; C, black; O, red; Zn, blue polyhedra. Hydrogen
atoms are omitted for clarity (5, 13, 34).
Fig. S3. A pcu net shown in augmented form and crystal structures of representative MOFs in its
net. The yellow sphere represents the size of the largest sphere that would occupy the cavity
without contacting the interior van der Waals surface. Zn, blue polyhedra; O, red; C, black; S,
yellow; Br, large green; N, green; I, large purple; Cu, large blue; all hydrogen atoms are omitted
for clarity. Interpenetrating frameworks are shown in light blue, orange, and light green.
Fig. S4. A qom net shown in augmented form and crystal structures of representative MOFs in
its net. The yellow sphere represents the size of the largest sphere that would occupy the cavity
without contacting the interior van der Waals surface. Zn, blue polyhedra; O, red; C, black; all
hydrogen atoms are omitted for clarity.
Fig. S5. A tbo net shown in augmented form and crystal structures of representative MOFs in its
net. The yellow sphere represents the size of the largest sphere that would occupy the cavity
without contacting the interior van der Waals surface. Metal ions, blue squares; O, red; C, black;
N, green; all hydrogen atoms and terminal ligands on the square units are omitted for clarity.
Interpenetrating frameworks are shown in light blue. Interpenetrating framework is shown in
light blue.
Fig. 6. A ntt net shown in augmented form and crystal structures of representative MOFs in its
net. The yellow sphere represents the size of the largest sphere that would occupy the cavity
without contacting the interior van der Waals surface. Cu and Zn, blue squares; O, red; C, black;
N, green; all hydrogen atoms and terminal ligands on the square units are omitted for clarity.
Fig. S7. Crystal structure of NU-110 and 108 along to the (111) direction (20, 48).
Fig. S8. An etb net shown in ball-and-stick form and crystal structures of representative MOFs
in its net. The yellow sphere represents the size of the largest sphere that would occupy the
cavity without contacting the interior van der Waals surface. Metal ions, green or blue polyhedra;
O, red; C, black; all hydrogen atoms and terminal ligands on the polyhedra are omitted for clarity.
Table S3: Summary of the Structures of MOFs
Material Chemical formula Inner diameter
(Å)
Pore aperture
(Å)
Density
(g/cm3)
Void fraction
(%) Ref.
MOF-5 Zn4O(BDC)3 15 8 0.59 79 13
MOF-200 Zn4O(BBC)2 18 × 28 16 0.22 90 17
MOF-210 (Zn4O)3(BTE)4(BPDC)3 27 × 48 13 0.25 89 17
MOF-399 Cu3(BBC)2 43 23 0.13 94 21
IRMOF-74-IX Mg2(DH9PhDC) 72 72 0.25 85 22
IRMOF-74-XI Mg2(DH11PhDC) 98 98 0.25 87 22
PCN-21 Cu2(PMTB) 37 13 0.42 82 170
mesMOF-1 Tb(TATB) 47 17 0.57 69 171
CMOF-4b Cu2(L) 32 × 24 32 × 24 0.18 92 172
UMCM-1 (Zn4O)3(BTB)4(BDC)3 23 23 0.39 85 173
UMCM-2 (Zn4O)3(BTB)4(T2DC)3 23 × 30 13 0.40 83 174
MIL-101c Cr3OF(H2O)2(BDC)3 26, 34 14 0.44 83 143
MIL-101-NDC Cr3O(OH)(H2O)2(NDC)3 33, 42 17 0.31 86 175
Bio-MOF-100 Zn4O(ad)2(BPDC)3 23 23 0.30 86 176
DUT-49 Cu2(BBCDC) 24 13 0.32 87 177
NU-110 Cu3(BHEHPI) 32 13 0.22 90 20
BDC2-
= benzenedicarbxylate, BBC3-
= 4,4′,4″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate, BTE3-
= 4,4′,4″-[benzene-1,3,5-triyl-
tris(ethyne-2,1-diyl)]tribenzoate, BPDC2-
= biphenyl-4,4′-dicarboxylate, DH9PhDC4-
= 2″″,5″″-dihexyl-
2′,2″,2‴ ,2‴ ″,2‴‴ ,2‴‴ ′,5′,5″,5‴ ,5‴ ″,5‴‴ ,5‴‴ ′-dodecamethyl-3,3‴‴ ″-dioxido-
[1,1′:4′,1″:4″,1‴ :4‴ ,1″″:4″″,1‴ ″:4‴ ″,1‴‴ :4‴‴ ,1‴‴ ′:4‴‴ ′,1‴‴ ″-noviphenyl]-4,4‴‴ ″-dicarboxylate, DH11PhDC4-
= 2‴ ,2‴‴ ′,5‴ ,5‴‴ ′-
tetrahexyl-3,3‴‴‴ ′-dioxido-2′,2″,2″″,2‴ ″,2‴‴ ,2‴‴ ″,2‴‴‴ ,5′,5″,5″″,5‴ ″,5‴‴ ,5‴‴ ″,5‴‴‴ -tetradecamethyl-
[1,1′:4′,1″:4″,1‴ :4‴ ,1″″:4″″,1‴ ″:3‴ ″,1‴‴ :4‴‴ ,1‴‴ ′:4‴‴ ′,1‴‴ ″:4‴‴ ″,1‴‴‴ :4‴‴‴ ,1‴‴‴ ′-undeciphenyl]-4,4‴‴‴ ′-dicarboxylate,
PMTB4-
= diphenyl-methane-3,3′,5,5′-tetrakis(3,5-bisbenzoate), TATB3-
= 4,4′,4″-s-triazine-2,4,6-triyltribenzoate, H4L = (R)-4,4′,4″,4‴ -
(1E,1′E,1″E,1‴ E)-2,2′,2″,2‴ -(2,2′-dihydroxy-1,1′-binaphthyl-4,4′,6,6′-tetrayl)tetrakis(ethene-2,1-diyl)tetrabenzoic acid, BTB3-
= 4,4′,4″-benzene-
1,3,5-triyl-tribenzoate, T2DC2-
= thieno[3,2-b]thiophene-2,5-dicarboxylate, NDC2-
= naphthalenedicarboxylate, ad- = adeninate, BBCDC
2- = 9,9′-
([1,1′-biphenyl]-4,4′-diyl)bis(9H-carbazole-3,6-dicarboxylate), BHEHPI6-
= 5,5′,5″-((((benzene-1,3,5-triyltris(benzene-4,1-diyl))tris(ethyne-2,1-
diyl))-tris(benzene-4,1-diyl))tris(ethyne-2,1-diyl))triisophthalate.
Table S4: Recent reports of post-synthetic modification of MOFs.
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Coordinative Interactions
Cu3(BTC)2 HKUST-1 Dehydration/ligand replacement on
SBU Water, pyridine
35
Cu3(BTC)2 HKUST-1 Dehydration/ligand replacement on
SBU Water, 4-(methylamino)pyridine 97% (best) Active site for NO capture 178
60% Active site for NO capture 178
Cu3(BTC)2 HKUST-1 Ligand exchange on SBU Dithioglycol
179
Cu2(ATC) MOF-11 Dehydration of SBU Water
30
Zn2(DOT) MOF-74(Zn) Ligand exchange/removal on SBU Water or ethanol
54
Co2(DOT) MOF-74(Co) Dehydration of SBU Water
Magnetic properties 138
Ni2(DOT) MOF-74(Ni) Dehydration of SBU Water
H2 storage investigated 139
Ni2(DOT) MOF-74(Ni) Ligand exchange on SBU Piperazine 25%
CO2 adsorption by
physisorption and
chemisorption
180
H3[Co6(TATB)4] PCN-9 Ligand exchange/removal on SBU Tetrabutylammonium, CO2
H2 and CH4 adsorption 181
H3[(Mn4Cl)3(BTT)8)] Mn-BTT Ligand exchange on SBU N,N-dimethylformamide (DMF),
methanol Enhanced H2 adsorption 144
H3(Cu4Cl)3(BTT)8 Cu-BTT Dehydration/ligand replacement on
SBU Water, methanol
Enhanced H2 adsorption 182
H3(Cu4Cl)3(BTT)8 Cu-BTT Ligand exchange on SBU Ethylenediamine
Enhanced CO2 uptake and
selectivity over N2 183
Fe3[(Fe4Cl)3(BTT)8]2 Fe-BTT Ligand exchange/removal on SBU DMF, methanol
184
NaNi3(OH)(SIP)2
Dehydration of SBU Water
H2 adsorption 185
Cr3O(H2O)3F(BTC)2 MIL-100(Cr) Dehydration/ligand replacement on
SBU Water, methanol
186,
187
Cr3O(H2O)2F(BDC)3 MIL-101(Cr) Ligand exchange on SBU
Ethylenediamine,
diethylenetriamine, 3-
aminopropyltrialkoxysilane
Catalyst for Knoevenagel
condensation 81, 186
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Cr3O(H2O)2F(BDC)3 MIL-101(Cr) Ligand replacement on SBU L-proline
Catalyst for asymmetric aldol
reactions 188
(Cr3O(H2O)2F(BDC-
NHBoc)4
MIL-101(Cr)-
NHBoc Ligand replacement on SBU Ethylenediamine
sequential deacetalization-
nitroaldol reaction 189
Zn2(BTetB)
Ligand exchange on SBU DMF, pyridine
CO2 and H2 adsorption
properties 190
Zn2(BTetB)
Ligand exchange on SBU DMF, trifluoromethyl, pyridine
Enhancement of CO2/N2
selectivity 191
Zn2(TCPBDA) SNU-30 Dehydration/ligand replacement on
SBU Water, BPTA
BPTA bridge neighboring
SBUs to form new MOF 192
Cd1.5(H3O)3[(Cd4O)3-
(HETT)8] Metal ion exchange Cd(II), Pb(II), Dy(III), Nd(III) 100%
Single-crystal-to-single-crystal
transformation involving
complete and reversible
exchange of metal ions in SBUs
193
Zn2(BDCPPI) SNU-50 Metal ion exchange Zn(II), Cu(II) 97%
Form PtS-type net with Cu(II),
which was not possible via
direct solvothermal synthesis
194
Mn(NDC)
Ligand removal on SBU N,N-Diethylformamide
Enhancement of N2, H2, CO2,
and CH4 uptake 195
Metalation
Cd3Cl6(L1)3
Metal Complexation within Pore Ti(OiPr)4
Catalyst in the addition of
ZnEt2 to 1-napthaldehyde with
complete conversion and 93%
ee.
67
Zn4O(BDC)3 MOF-5 Organometallic complexation of
BDC Cr(CO)6
Photolysis used to substitute
single CO ligand per metal site
for N2 or H2
196
In2(HImDC)4 rho-ZMOF Metalation of ligand
5,10,15,20-tetrakis(1-methyl-4-
pyridinio)-porphyrin tetra(p-
toluenesulfonate) (H2RTMPyP),
Mn(II)
Catalyst for cyclohexane
oxidation with 91.5% product
yield.
78
Zn4O(BDC-NH2)3 IRMOF-3 Metal complexation within pore V(O)(acac)2
Catalyst for oxidation of
cyclohexene with tBuOOH
(40% conversion)
197
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Zn4O(BDC-NH2)3 IRMOF-3 Metal complexation within Pore NaAuCl4 ~2 wt%
Used for three-component
coupling and cyclization of N-
protected ethylaniline,
aldehyde, and amines
198
Zn4O(BDC-NH2)3 IRMOF-3 Imine condensation metalation Mn(acac)2 ~8% Catalyst for epoxidation of
alkenes 199
Zn4O(dimethylthioethyl
enethio-BDC)3
Metalation of
methylthioethylenethio groups HgCl2 ~12%
Removal of HgCl2 from an
ethanol solution 200
Al(OH)(BDC-NH2) MIL-53(Al)-NH2 Metalation of hydroxide groups in
SBU 1,1'-Ferrocenediyl-dimethylsilane ~25%
Redox catalyst for the oxidation
of benzene with H2O2 201
Fe3O(H2O)2F(BDC)3 MIL-101(Fe) Metalation through acylation of
amine functionality
cisplatin prodrug, c,c,t-
[PtCl2(NH3)2(OEt)(O2CCH2CH2C
O2H)]
~40% Utilized for cytotoxicity studies
on cancer cell lines 202
Pb3(TMBD)3 PbTMBD Metalation of thioether
functionality HgCl2
203
Zn2(TCPB)(DPG) DO-MOF
Esterification with metal
complexation of free carboxylate
groups
CuCl2
204
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2
Metal complexation of
iminopyridine moiety PdCl2
205
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2 Metal complexation Fe(acac)3, Cu(acac)2 50%
Fe(salicylate) complex
catalyzes Mukaiyama aldol
reactions (58% conversion after
24 hrs)
68
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2 Metal complexation In(acac)3 3.76 wt%,
Selective catalyst for epoxide
ring opening reactions 206
2.92 wt%
206
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2 Metal complexation Fe(III)
207
Zr6O4(OH)4(BDC)6 UIO-66 Organometallic complexation Cr(CO)6 1 wt%
Photolysis used to substitute
single CO ligand per metal site
for N2
208
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Zn2(L2) and Zn2(L3)
Metalation Ti(IV)
Heterogeneous asymmetric
Catalysis 209
Al(OH)(BPyDC) MOF-253 Metalation of 4,4'-bipyridine linker Cu(II), Pd(II) >80% Increased selectivity for CO2/N2 210
Zn2(TCPB)(Mn(III)(sal
en)) MnSO-MOF Demetalation from link Mn(III) 90%
Selectively removed from
surface of MOF 211
Zn4O(TATAB)2 PCN-100 Metalation of TATAB linker Co(NO3)2, Cd(NO3)2, or HgCl2 40-43% Capture of heavy metal ions 212
Zn(mBDC)(L4)
single-crystal-tosingle-crystal post-
synthetic modification Cu(BF4)2
213
Covalent Bond Formation
Zn4O(BDC-NH2)3 IRMOF-3 Amide coupling with free amine Acetic anhydride >80%
6
Zn4O(BDC-NH2)3 IRMOF-3 Amide coupling with free amine 10 linear anhydrides 97%-11%
214
Zn4O(BDC-NH2)3 IRMOF-3 Amide coupling with free amine Crotonic anhydride, acetic
anhydride Tandem modification proven 215
Zn4O(BDC-NH2)3 IRMOF-3 Amide coupling with free amine Various functionalized anhydrides Up to 99%
216
Zn4O(BDC-NH2)3 IRMOF-3 Amide coupling with free amine Benzoic anhydride 70% Increased H2 gravimetric uptake
at 77 K and 1 atm 66
Zn4O(BDC-NH2)3 IRMOF-3 Amide coupling with free amine Nicotinoyl chloride, pyridine 50%
Catalyst for aza-Michael
reaction and transesterification
of ethyldecanoate with
methanol
217
Zn4O(BDC-NH2)3 IRMOF-3 Amide coupling with free amine Isobutyric anhydride 88% Increase in hydrophobicity and
stability of framework 218
Zn4O(BDC-NH2)3 IRMOF-3 Imine condensation of free amine Salicylaldehyde 13%
197
Zn4O(BDC-NH2)3 IRMOF-3 Imine condensation of free amine Salicylaldehyde 3%
Metalation followed by
catalysis three-component
coupling and cyclization of N-
protected ethylaniline,
aldehyde, and amines
198
Zn4O(BDC-NH2)3 IRMOF-3 Imine condensation of free amine Mn(acac)2 ~8% Catalyst for epoxidation of
alkenes 199
Zn4O(BDC-NH2)3 IRMOF-3 Urea formation of free amine Various isocyanate derivatives ~99%
219
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Zn4O(BDC-NH2)3 IRMOF-3 Amide coupling/urea formation
through free amine Various isocyanate derivatives 32%
216
Zn4O(BDC-NH2)3 IRMOF-3 Urea formation through free amine Phenyl isocyanate 41%
Increased H2 wt% uptake at 77
K and 1 atm in comparison to
parent IRMOF-3
66
Zn4O(BDC-NH2)3 IRMOF-3 Thiourea formation through free
amine Fluorescein-isothiocyanate
Confocal Microscopy used to
probe the distribution of
fluorescent dyes encapsulated
within the MOF
220
Zn4O(BDC-NH2)3 IRMOF-3 Halogenation Bromine
215
Zn4O(BDC-NH2)3 IRMOF-3 Ring-opening reaction through
Free Amine
1,3-Propanesultone and 2-
methylaziridine 57%
221
Zn4O(BDC-NH2)3 IRMOF-3 Formation of N-diazenium diolates
from free amine Nitric oxide 8%
222
Zn4O(BDC-NH2)3 IRMOF-3 Reaction of cyanuric chloride with
amine Cyanuric chloride
CO2 breakthrough testing 223
Zn4O(BDC-NH2)3 IRMOF-3 Conversion of primary amines into
secondary amines Various aldehyde, NaBH3CN 31-67%
224
Zn4O(BDC-NH2)4 IRMOF-3 Vapor-phase post-synthetic
modification Salicylic acid >99%
225
Zn4O(BPDC)3 IRMOF-9 Imine Condensation through free
aldehyde Dinitrophenylhydrazine 50-60%
226
Zn4O(BPDC)3 IRMOF-9 Oxidation of sulfur-tagged BPDC Dimethyldioxirane 100% First example of oxidation
postsynthetic modification 227
Zn4O(BPDC)3 IRMOF-9 Deprotection of Boc-protected
amine Thermolysis
228
Zn4O(BPDC-
C5H8ON2)3 IRMOF-9-Pro-Boc
Deprotection of amide-coupled
Boc-protected proline unit Thermolysis
Chiral organocatalyst for aldol
reaction 229
Zn4O(TPDC-(CH2N3)2)3 IRMOF-16-N3 Click reaction through free azide Alkynes of varying lengths and
sizes 230
Zn4O(BPDC-
(CH2N3)2)4 IRMOF-10-N3 Click reaction through free azide
Conversion of azide to primary
amine via Staudinger reaction 231
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Gd2(BDC-NH2)3 MOF-LIC-1 Amide coupling with free amine Acetic Anhydride 50%
232
(ZnI2)3(L5)2(L6)
Amide coupling with free amine Various anhydride derivatives
233
Zn2(BDC-
NH2)2(DABCO) DMOF-1-NH2 Amide coupling with free amine
Various anhydrides with differing
lengths, trimethylacetic anhydride
and isobutyric anhydride
99% - 0%
135
Zn2(BDC-
NH2)2(DABCO) DMOF-1-NH2
Click reaction through free azide
converted from amine Phenylacetylene >90% One-pot modification 234
Zn2(BDC-
NH2)2(DABCO) DMOF-1-NH2 Amide coupling with free amine Benzoic anhydride 63% No enhanced H2 properties 96
Zn2(TDC)2(L7)
Epoxidation and subsequent
epoxide ring-opening
3-(But-3-en-1-yl)-3‟-methyl-4,4‟-
bipyridine, ethyl mercaptan 235
51Zn6(BTB)4(BPy-
NH2)3
Thiourea formation from
isothiocyanate Fuorescein isothiocyanate 7.50%
Selective sensing and
adsorption of Ag+ 236
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2 Amide coupling with free amine
Various anhydrides with differing
lengths, trimethylacetic anhydride
and isobutyric anhydride
99% - ~1%
135
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2 Amide coupling with free amine Benzoic anhydride 76%
Increased H2 uptake at 77 K and
1atm 66
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2 Amide coupling with free amine
3-Hydroxyphthalic anhydride,
2,3-pyrazinedicarboxylic
anhydride
35%, 50% Used for subsequent metal
complexation 206
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2 Imine condensation of free amine 2-Pyridinecarboxyaldehyde
Iminopyridine moiety metalated
with PdCl2 205
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2
Ring-opening reaction using free
amine
3-Hydroxyphthalic anhydride,
2,3-pyrazinedicarboxylic
anhydride
35%, 50% Used for metal complexation 68
(Zn4O)3(BDC-
NH2)3(BTB)4 UMCM-1-NH2
Formation of N-diazenium diolates
from free amine Nitric oxide 6%
222
Al(OH)(BDC-NH2) MIL-53(Al)-NH2 Amide coupling with free amine Formic acid
237
Al(OH)(BDC-NH2) MIL-53(Al)-NH2 Amide coupling with free amine Acetic anhydride, long chain
alkyl anhydrides 91%-17%
Enhanced hydrophobicity of the
MOF 218
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Al(OH)(BDC-NH2) MIL-53(Al)-NH2 Urea and thiourea formation from
Iso(thio)cyanate Various primary amines >90% - 0%
238
Al(OH)(BDC-NH2) MIL-53(Al)-NH2 Ring-opening reaction using free
amine Maleic and succinic anhydrides 43%, 40%
Organocatalyst for
methanolysis of cis-2,3-
epoxybutane and other epoxides
239
Al(OH)(BDC-NH2) MIL-53(Al)-NH2 Iso(thio)cyanate formation from
free amine Diphosgene, thiophosgene 90% Increased CO2 uptake 238
Al(OH)(BDC-NH2) MIL-53(Al)-NH2 (Thio)carbamate formation from
Iso(thio)cyanates Various primary alcohols >95% - ~65%
238
Al(OH)(BDC-NH2) MIL-53(Al)-NH2 Amide coupling with free amine Ferrocenecarboxylic anhydride
Cyclic voltammetry 240
Fe3O(H2O)2F(BDC)3 MIL-101(Fe) Acylation
Cisplatin prodrug, c,c,t-
[PtCl2(NH3)2(OEt)(O2CCH2CH2C
O2H)]
~40% Utilized for cytotoxicity studies
on cancer cell lines 202
Cr3O(H2O)2F(BDC)3 MIL-101(Cr) Urea formation from free amine Ethyl isocyanate 100% Multi-step post synthetic
modification 241
Cr3O(H2O)2F(BDC)3 MIL-101(Cr) Reduction of NO2-functionalized
BDC Tin(II) Chloride in Ethanol
Multi-step post synthetic
modification 241
Cr3O(H2O)2F(BDC)3 MIL-101(Cr) Alkylation of incorporated Amine-
functionalized BDC
1,3,5,7-Tetramethyl-4,4-difluoro-
8-bromomethyl-4-bora-3a,4a-
diaza-s-indacene (Br-BODIPY)
40.3% Integration of imaging
component 32
Cr3O(H2O)2F(BDC)3 MIL-101(Cr) Electrophilic Aromatic Substitution
of BDC HNO3
241
Cr3O(H2O)2F(BDC-
NH2)3 MIL-101(Cr)-NH2 Amide coupling with free amine p-phenylazobenzoylchloride
UV/Vis switching experiments,
methane adsorption 242
Cr3O(H2O)2F(BDC-
NH2)3 MIL-101(Cr)-NH2 Urea formation from free amine 4-(phenylazo)phenylisocyanate
UV/Vis switching experiments,
methane adsorption 242
Cr3O(H2O)2F(BDC-
NHBoc)4
MIL-101(Cr)-
NHBoc
Deprotection of amide-coupled
Boc-protected proline unit Thermolysis
sequential deacetalization-
nitroaldol reaction 189
Zr6O4(OH)4(BDC-
NH2)12 UIO-66-NH2 Amide coupling with free amine
Acetic, valeric, octanoic, maleic
anhydride 25-88%
243,
244
Zr6O4(OH)4(BDC-Br)12 UIO-66-Br Cyanation of Br-functionalized CuCN in N-methyl-2-pyrrolidone 90%
245
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
ZnF(Am2TAZ)
Amide coupling with free amine Nicotinoyl chloride, pyridine 60%
Catalyst for aza-Michael
reaction and transesterification
of ethyldecanoate with
methanol
217
Zn(ICA)2 ZIF-90
Imine Condensation of
Carboxyaldehyhde-functionalized
Link
Ethanolamine 100%
69
Zn(ICA)2 ZIF-90 Imine condensation of free
aldehyde 3-Aminopropyltriethoxysilane
Used as molecular sieve with
high H2 permselectivity 246
Zn(ICA)2 ZIF-90 Reduction of aldehyde-
functionalized link Sodium borohydride 80%
69
Zn(MICA)2 SIM-1 Imine condensation of aldehyde-
functionalized link Dodecylamine
Catalyst for Knoevenagel
condensation 247
(ZnI2)3(L5)2(L8)
Imine condensation of amine-
functionalized imbedded link Acetaldehyde 60%
248
(ZnI2)3(L5)2(L8)
Imine condensation of amine-
functionalized imbedded link Acetaldehyde 36%
Observed transient hemiaminal
intermediate by single crystal x-
ray diffraction techniques
249
(ZnI2)3(L5)2(L6)
Imine condensation of
carboxyaldehyde-functionalized
imbedded link
Aniline, aminobenzoic acid
233
Zn3( 3-O)(D-PTT)6 POST-1 N-alkylation of free pyridyl groups Iodomethane 100%
Changes framework charge
from negative to positive, and
makes it possible for reversible
exchange of counterions
172
Zn4O(trans-4,4′-stilbene
dicarboxylate)3 Halogenation of stilbene units Bromine 60%
Stabilization of framework with
corresponding increase in
measured porosity, lack of
significant hysteresis, and
retention of crystallinity
250
Zn3(TCPB)(L9) TO-MOF Click Reaction of Terminal
Alkynes Benzyl azide
251
Al4(OH)2(OMe)4(BDC-
NH2)3 CAU-1-NH2 Amide Coupling with Free Amine acetic anhydride
CO2 and water adsorption
properties 252
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
(L10)·AgOTf
Silylation of Free Alcohol Groups Silyl Triflates
253
(L11)·AgOTf
Esterification of Free Alcohol
Groups Trifluoroacetic anhydride
254
Cu3(TATB)2 mesoMOF-1 Protonation of ionic framework HF, HCl, HBr
Stabilization of mesochannels 36
Ni2(L-asp)2(BPy)
Protonation of ionic framework HCl
Catalyst for methanolysis of
cis-2,3-epoxybutane (<17% ee
values and 2.6 turnover
frequency
255
Zn2(mBDC-N3)2(BPy)2 CID-N3 Oxidation to reactive triplet nitrene
functionality O2
Increased uptake of O2,
specifically in low pressure
region
256
Metal Doping
Zn4O(BDC)3 MOF-5 Physical mixture Pt on Activated Carbon
Enhanced hydrogen storage via
spillover mechanism
(enhancement factor of 3.3)
257
Zn4O(BDC)3 MOF-5 Impregnation Pd nanoparticles ~1 wt%
Catalyst for hydrogenation of
styrene and showed enhanced
H2 uptake capacity
258
Zn4O(BDC)3 MOF-5 Gas-phase loading 1.5-1.7 nm Ru nanoparticles 30 wt% Catalyst for alcohol oxidation,
hydrogenation of benzene 259
Zn4O(NDC)3 IRMOF-8 Physical mixture Pt on activated carbon
Enhanced hydrogen storage via
spillover mechanism
(enhancement factor of 3.1 to
1.8 wt% at 298 K and 10 MPa)
257
Zn4O(BTB)2 MOF-177 Gas-phase loading 2-5 nm Pt nanoparticles 43 wt% Catalyst for oxidation of
alcohols 260
Al3O(H2O)3F(BTC)2 MIL-100(Al) Impregnation 2 nm Pd nanoparticles 10 wt % Excess H2 adsorption was
doubled at room temperature 261
Cr3O(H2O)2F(BDC)3 MIL-101(Cr) Inclusion [Mo6Br8F6]2- cluster units
262
Zn2(TCPB)(DPG) DO-MOF Metal Alkoxide formation from
free diol groups Li+ and Mg2+
Variable
loadings
Slightly higher H2 wt% uptake
(1.32 wt% for Li in comparison
to 1.23 wt% for parent MOF at
77 K and 1 atm)
263
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Zn2(NDC)2(diPyNI)
Reduction of Redox Active diPyNI
link Li metal 5 mol%
Nearly doubled H2 capacity
(0.93 wt% H2 capacity of parent
MOF to 1.63 wt% of PSM
MOF) at 77 K and 1 atm
263
Zn2(NDC)2(diPyNI)
Reduction of redox AActive
diPyNI link Na and K metal
Enhanced H2 capacity (at low
pressure and temperature). Up
to 65% higher H2 uptake than
neutral framework
264
Ligand Exchange
Zn2(BDC-
NH2)2(DABCO) DMOF-1-NH2
Ligand Exchange through
Selective Surface Modification Boron dipyrromethene (BODIPY)
265
Cu3(BTC)2 HKUST-1 Ligand exchange through selective
surface modification Boron dipyrromethene (BODIPY)
265
Cation Exchange
Zn8(ad)4(BPDC)6O BIO-MOF-1 Cation exchange of DMA cations
within pores
Lanthanide Cations [Sm(III),
Ln(III), Eu(III), Tb(III)]
Enahanced luminescence
properties 266
Zn8(ad)4(BPDC)6O BIO-MOF-1 Cation exchange of DMA cations
within pores
Tetramethylammonium,
Tetraethylammonium,
Tetrabutylammonium
Enhanced CO2 adsorption at
273 K and an increase in the
isoteric heat of adsorption of
CO2
266
Photochemical Modification
(Zn4O)3(BDC-
(NO2BnO)2)3(BTB)4
UMCM-1-
OBnNO2
Cleavage of protecting groups by
UV irridiation at 365 nm 100%
207
(Zn4O)3(BDC-
(NO2BnO)2)3(BTB)4
UMCM-1-
(BnNO2)2
Cleavage of protecting groups by
UV irridiation at 365 nm 75%
207
Zn2(mBDC-N3)2(BPy)2 CID-N3 Irridation to produce reactive
triplet nitrene Hg Lamp 70%
Exposed reactive nitrene
functionalities to O2 and CO to
demonstrate increased uptake as
a result of PSM
256
Zn4(μ3-OH)2(5-
SIPA)2(1,4-BPEB)2
Regioselective [2+2]
photodimerization of BPEB links
to generate dicyclobutane link
Hg Lamp
Single-crystal-to-single-crystal
transformation induced by
photochemical modification
267
Chemical Formula Parent MOF
Common Name Reaction Type Reactants Used
Percent
Conversion Application/Use Ref.
Cd2(1,3-PDA)2(1,4-
BPEB)2
Regioselective [2+2]
photodimerization of BPEB links
to generate dicyclobutane link
Hg Lamp
Single-crystal-to-single-crystal
transformation induced by
photochemical modification
267
Zn(BPE)(MUCO)
Regioselective [2+2]
Photodimerization of bpe Links to
Generate Dicyclobutane Link
Xe Lamp 100%
268
Zn(BPE)(BDC)
Regioselective [2+2]
Photodimerization of bpe Links to
Generate Dicyclobutane Link
Xe Lamp 100%
268
Zn(BPE)(FUM)
Regioselective [2+2]
Photodimerization of bpe Links to
Generate Dicyclobutane Link
Xe Lamp
268
Core-Shell Structure
Zn4O(BDC-NH2)3 IRMOF-3 Core-Shell Single Crystal
Fabrication Zn4O(BDC)3 (MOF-5)
Demonstration of a three-layer
core-shell structure of
alternating layers of MOF-
5@IRMOF-3@MOF-5 were
shown to be possible
269
Zn4O(BDC-NH2)3 IRMOF-3 Core-shell single crystal
fabrication Zn4O(BDC)3 (MOF-5)
Heteroepitaxially Grew
IRMOF-3 around MOF-5 as a
thin film
270
Zn2(NDC)2(DABCO)
Core-shell single crystal
fabrication Cu2(NDC)2(DABCO)
Zn2(NDC)2(DABCO) chosen as
the core and Cu2(NDC)2-
(DABCO) used as the shell.
Nitrogen pilllar ligands of Zn
MOF were used as coordination
sites for epitaxial growth
130
Zn2(NDC)2(DPNDI)
Core-shell single crystal
fabrication Zn2(NDC)2(DPNDI)
Zn2(NDC)2(DPNDI) used as the
shell. Nitrogen pilllar ligands of
the core MOF were used as
coordination sites for epitaxial
growth
271
M6(BTB)4(BPy)3
Core-shell single crystal
fabrication Zn, Co, Ni, and Cu nitrate
Demonstration of enhanced
framework stabilities by
transmetalations of the
framework metal ions
272
BTC3-
= benzenetricarbxylate, ATC4-
= 1,3,5,7-adamantane tetracarboxylate, DOT4-
= 2,5-dioxidoterephthalate, TATB3-
= 4,4′,4″-s-triazine-2,4,6-
triyltribenzoate, BTT3-
= 1,3,5-benzenetristetrazolate, SIP2-
= 5-sulfoisophthalate, BDC2-
= benzenedicarbxylate, BTetB4-
= 4,4′,4″,4‴ -benzene-
1,2,4,5-tetrayltetrabenzoate, H4TCPBDA = N,N,N′,N′-tetrakis(4-carboxyphenyl)biphenyl-4,4′-diamine, BPTA = 3,6-di(4-pyridyl)-1,2,4,5-tetrazine,
H3HETT = 5,5′,10,10′,15,15′-hexaethayltruxene-2,7,12-tricarboxylic acid, H4BDCPPI = N,N′-bis(3,5-dicarboxyphenyl)pyromellitic diimide,
NDC2-
= naphthalenedicarboxylate, L1 = (R)-6,6′-dichloro-2,2′-dihydroxy-1,1′-binaphthyl-4,4′-bipyridine, H3ImDC = 4,5-imidazoledicarboxylic
acid, H2TMBD = tetrakis(methylthio)-1,4-benzenedicarboxylic acid, H4TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene, DPG = meso-1,2-
bis(4-pyridyl)-1,2-ethanediol, BTB3-
= 4,4′,4″-benzene-1,3,5-triyl-tribenzoate, L24-
= (R)-2,2′-diethoxy-1,1′-binaphthyl-4,4′,6,6′-tetrabenzoate,
L34-
= (R)-2,2′-dihydroxy-1,1′-binaphthyl-4,4′,6,6′-tetrabenzoate, H2BPyDC = 2,2′-bipyridine-5,5′-dicarboxylic acid, Mn(III)(salen) = (R,R)-(–)-
1,2-cyclohexanediamino-N,N′-bis(3-tert-butyl-5-(4-pyridyl)salicylidene)Mn(III)Cl, TATAB3-
= 4,4′,4″-((1,3,5-triazine-2,4,6-
triyl)tris(azanediyl))tribenzoate, mBDC2-
= isophthalate, L4 = N,N′-bis(pyridin-4-yl)-2,2′-bipyridine-5,5′-dicarboxamide, BPDC2-
=
biphenyldicarboxylate, TPDC2-
= terphenyldicarboxylate, L5 = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine, L6 = triphenylen-2-amine, DABCO = 1,4-
diazabicyclo[2.2.2]octane, H2TDC = 9,10-triptycenedicarboxylic acid; L7 = 3-(but-3-en-1-yl)-3′-methyl-4,4′-bipyridine, Am2TAZ- =
diaminotriazolate, ICA- = imidazolate-2-carboxyaldehyde, HMICA = 4-methyl-1H-imidazole-5-carbaldehyde, L8 = triphenylen-1-amine, D-PTT
-
= (4S,5R)-2,2-dimethyl-5-(1-(pyridin-4-ylamino)vinyl)-1,3-dioxolane-4-carboxylate, L9 = 4-(2-(pyridin-4-yl)vinyl)-3-
((trimethylsilyl)ethynyl)pyridine, L10 = 2,4,6-tris(4-((4-cyanophenyl)enthynyl)phenylethynyl)phenoxy)-ethanol, L11 = (2,4,6-tris(4-
ethynylbenzonitrile)phenoxy)ethanol, L-asp- = L-aspartate, BPy = 4,4′-bipyridine, DPG = 1,2-di(pyridin-4-yl)ethane-1,2-diol, diPyNI = N,N′-di-
(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide, ad- = adeninate, H3SIPA = 5-sulfoisophthalic acid, BPEB = 1,4-bis[2-(4-
pyridyl)ethenyl]benzene, H2PDA = 1,3-phenylenediacetic acid, BPE = 1,2-bis(4-pyridyl)ethane, H2MUCO = trans,trans-muconic acid, FUM- =
fumarate.
Table S5: Recent reports of MOF based catalysts.
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
Cd(BPy)2(NO3)2
Benzaldehyde and cyanotrimethylsilane Cyanosilylation of aldehyde 77%
29
Gd(R-L1H2)(R-L1H3)(H2O)4
benzaldehyde, propionaldehyde, 1-
naphthaldehyde, and trimethylsilyl cyanide Cyanosilylation of aldehyde 55-69% <5% 273
Cu3(BTC)2
Benzaldehyde and cyanotrimethylsilane Cyanosilylation of aldehyde 57%
274
Mn3[(Mn4Cl)3(BTT)8]2
Benzaldehyde and cyanotrimethylsilane Cyanosilylation of aldehyde 98%
62
Zn(HPTA)
4-Nitrobenzaldehyde and
cyanotrimethylsilane Cyanosilylation of aldehyde 92%
275
Sc2(C4O4)3
Benzaldehyde, acetophenone Cyanosilylation of aldehyde 45-90%
276
Ce(MDIP)(H2O) Ce-MDIP1 2-Naphthaldehyde and cyanotrimethylsilane Cyanosilylation of aldehyde >98% >98% 277
Zn(3,3′-TPBC)(DABCO)0.5
4-Nitrobenzaldehyde and nitroalkanes Henry reaction of 4-nitrobenzaldehyde 12-80%
278
Cd(BTAPA)2(NO3)2
Benzaldehyde and malononitrile Knoevenagel condensation 98%
279
Zn4O(BDC-NH2)3 IRMOF-3 Benzaldehyde and ethyl cyanoacetate Knoevenagel condensation 99%
280
Cr3O(H2O)2F(BDC)3 MIL-101(Cr) Benzaldehyde and ethyl cyanoacetate Knoevenagel condensation 98%
281
Zn(HPTA)
4-Nitrobenzaldehyde and ethyl 2-
cyanoacetate Knoevenagel condensation 80%
275
Zn4O(TATAB)2 PCN-100 Butyl cyanoacetate, benzaldehyde, and 4-
phenylbenzaldehyde Knoevenagel condensation 58-93% 212
Zn4O(BTATB)2 PCN-101 Butyl cyanoacetate, benzaldehyde, and 4-
phenylbenzaldehyde Knoevenagel condensation 65-96% 212
[(iPrO)TiCl]2(L2)
Acrolein and 1,3-cyclohexadiene Diels-Alder reaction 100%
282
Gd(R-L1H2)(R-L1H3)(H2O)4
Methyl acrylate cyclopentadiene Diels-Alder reaction 86% <5% 273
Acid-activated Fe3O(H2O)3F(BTC)2 MIL-100(Fe) 1,3-Cyclohexadiene, dimethyl fumarate,
Methyl acrylate, Methacrolein, Acrolein Diels–Alder reactions 21-81%
283
Ti/Cu2(DDBD)(H2O)2 Ti/(S)-KUMOF-
1 Danishefsky‟s diene and benzaldehyde Hetero Diels–Alder reactions 52-80% 33-55% 284
Cd(BTB)(L-IP)(H2O)4 Cd-TBT 4-Nitrobenzaldehyde and cyclohexanone Aldol reactions 97% 58% 285
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
Zn4O(BPDC-C5H8ON2)3 IRMOF-Pro 4-Nitrobenzaldehyde and acetone Aldol reactions
29% 229
Cu3(BTC)2
2-Hydroxy-5-methylbenzaldehyde and ethyl
3-formyl-6-methyl-2-oxo-4-phenyl-1,2,3,4-
tetrahydropyrimidine-5-carboxylate
derivatives
Aldol reactions 30-87%
285
(Zn4O)3(BTB)4(BDC-
C8H5O4NFe(III))3
UMCM-1-
AMFesal
Naphthaldehyde, mesitaldehyde, and 1-
methoxy-2-methyl-1-(trimethylsiloxy)
Propene
Mukaiyama-aldol reactions 53-70%
68
Zn4O(BDC)3 MOF-5 Biphenyl and toluene Friedel-Crafts alkylation reactions 40-73%
286
Zn3(OH)2(BPDC)2 MOF-69A Biphenyl and tert-butyl chloride Friedel-Crafts alkylation reactions 10-33%
286
Zn4O(BDC)3 MOF-5 Toluene and benzyl bromide Friedel–Crafts alkylation reactions >99%
287
Zn4O(BDC)3 IRMOF-1 tert-Butylchloride and toluene Friedel-Crafts alkylation 60-80%
288
Zn2(L3)(BPY)2 NU-601 N-methylpyrrole and (E)-1-nitroprop-1-ene Friedel−Crafts reactions between
pyrroles and nitroalkenes 98%
289
Pd(PYMO)2
Phenylboronic acid and 4-bromoanisole Suzuki-Miyaura coupling 74-90%
290
Pd Al(OH)(BDC-NH2) Pd/MIL-53(Al)-
NH2 Bromobenzene and phenylboronic acid Suzuki-Miyaura coupling 29-97%
291
Cu(PdCl2BPy)
Phenyl halides and arylboronic acid Suzuki-Miyaura coupling 75-99%
292
Pd Zn4O(BDC)3 Pd@MOF-5 Phenylacetylene and iodobenzene Sonogashira coupling reaction 3-98%
293
Pd EDTA-MIL-101(Cr) Pd-DETA-MIL-
101(Cr) Acrylic acid, triethylamine, and iodobenzene
Heck reactions of acrylic acid and
Iodobenzene 13-36%
294
Cu(SO4)(PBBM)
2,6-Dimethylphenol Oxidative coupling of dimethylphenol 85%
75
(Cu(Ac)2(PBBM))(CH3OH)
2,6-Dimethylphenol Oxidative coupling of dimethylphenol 90%
75
Gd(R-L1H2)(R-L1H3)(H2O)4
meso-2,3-Dimethylsuccinic anhydride and
trimethylsilyl cyanide Ring Opening of Cyclic Anhydrides 81% <5% 273
(R)-Cu2(5,5′-BDA)2(H2O)2
Epoxide, aniline, toluene Ring-opening reaction of epoxide 15-54% 43-45% 295
(Zn4O)3(BDC-C8H5O4NIn)3(BTB)4 UMCM-1-
AMInsal 2-Phenyloxirane and aniline Epoxide ring-opening reactions 99%
206
Cu(BPy)(H2O)2(BF4)2(BPy)
2-Methyl-2-phenyloxirane and methanol Ring-opening of epoxides 99%
296
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
Cu2(L-asp)2(BPE)
cis-2,3-Epoxybutane and methanol Methanolysis of epoxide 30-59% 10-17% 255
Cu2(L-asp)2(BPE)
cis-2,3-Epoxybutane and methanol Methanolysis of epoxide 32-65% 6-13% 255
Cu(BPy)(H2O)2(BF4)2(BPy)
Styrene, methanol, 2-propanol, tert-buthanol Alcoholysis of epoxide 4-93%
297
Zn4O(BDC)3-x(BDC-NH2)x
Propylene oxide, CO2, and
tetraalkylammonium halides Formation of propylene carbonate 0-89%
298
Zn2(TCPB)(Mn(III)(salen)) Mn(III)SO-MOF Ethyl 4-vinylbenzoate and 2-(tert-
butylsulfonyl)iodosylbenzene Epoxidation reaction 40% 80% 211
Zn2(TCPB)(Mn(II)(salen)) Mn(II)SO-MOF 2,2-Mimethyl-2H-chromene and 2-(tert-
butylsulfonyl)iodosylbenzene Epoxidation reaction
299
Sc2(NDS)(OH)4, Y(1,5-
NDS)(OH)(H2O) RPF-12, 13, 14 Linalool Epoxidation of linalool 62-100%
300
Ln(OH)(1,5-NDS) LnPF-1 Linalool Epoxidation of olefin 76-100%
301
Ln2(N3)(NIC)2(OH)3(HNIC)(H2O),
(Y(III), Gd(III))
Cyclooctene, styrene, 4-methylstyrene,
3-methylstyrene, 1-hexene, and tert-butyl
hydroperoxide
Epoxidation of olefins 41-99%
302
Sm4(N3)2(NIC)4(OH)6(HNIC)2
(H2O)2
Cyclooctene, styrene, 4-methylstyrene,
3-methylstyrene, 1-hexene, and tert-butyl
hydroperoxide
Epoxidation of olefins 40-99%
302
Zn2(BPDC)2(Mn(III)(salen))
2,2-Dimethyl-2H-chromene and 2-(tert-
butylsulfonyl)iodosylbenzene Epoxidation of olefins 71% 82% 303
(Mn(TpCPP)Mn1.5)(C3H7NO) PIZA-3 Cyclic alkenes Epoxidation of olefin 20-74%
76
Co2(H2O)(H2O)4(Co-DCDPD) MMPF-3 stilbene and tert-butyl hydroperoxide Epoxidation of stilbene 96%
304
Co(HOBA)2
Styrene, 4-Chlorostyrene, 4-tert-Butylstyrene,
Ethyl cinnamate, trans-Stilbene Epoxidation of olefins (solvent-free) 47-96%
305
Co(L4)2(H2O)4
Olefins and isobutyraldehyde Aerobic epoxidation of olefin 37-66%
306
Cu(L4)2(H2O)2
Olefins and isobutyraldehyde Aerobic epoxidation of olefin 48-74%
307
Pt Zn4O(BTB)2 Pt@MOF-177 2-Chlorobenzyl alcohol Oxidation of alcohol 99%
260
Pd(PYMO)2
Cinnamyl alcohol Oxidation of alcohol 99%
290
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
Mn-TMPyP [In48(HImDC)96] Cyclohexane and tert-butylhydroperoxide Oxidation of alkane 92%
78
(Mn2(TpCPP)2Mn3)(C3H7NO)2 PIZA-3 Cyclic alkanes, iodosylbenzene Oxidation of alkane 48-53%
76
Zn2(L5-Zn)(L6-Mn) ZnMn-RPM Cyclohexane and 2-(tert-
butylsulfonyl)iodosylbenzene Oxidation of cyclohexane
298
[PW11TiO39] MIL-101 α-Pinene and H2O2 Oxidation of olefin 40%
79
[PW11CoO39] MIL-101 α-Pinene and O2 Oxidation of olefin 45%
79
Structure is not determined In-Mn(III)-
porphyrin MOF
Styrene and 2-(tert-
butylsulfonyliodosyl)benzene Oxidation of olefin
308
(Zn4O)(BDC-NH2)2.6(BDC-
C7H5NO-VO-acac)0.4
IRMOF-3-
Vsal0.4 Cyclohexene and BuOOH Oxidation of olefin
197
Cu(H2BTEC)(2,2′-BPy)
Cyclohexene, styrene Oxidation of olefins 6-65%
309
Ln(OH)(NDS)(H2O) LnPF-1 Acetonitrile, H2O2 Oxidation of linalool 75-100% 310
Sc2(NDS)(OH)4, Y(1,5-
NDS)(OH)(H2O) RPF-12, 13, 14 Methylphenylsulfide, H2O2 Oxidation of sulfides 100%
300
Ru Zn4O(BDC)3 Ru + MOF-5 Benzyl Alcohol and O2/Ar Oxidation of Benzyl Alcohol 25%
259
Fe3O(H2O)3F(BTC)2 MIL-100(Fe) Diphenylmethane and tert-
butylhydroperoxide Oxidation of diphenylmethane 48%
311
Zr3O4(Fe(III)Cl-TCPP) PCN-222(Fe) Pyrogallol and hydrogen peroxide Oxidation of pyrogallol
312
Al(OH)(BDC-NH2)SiMe2Fc MIL-53-NH2 Benzene, H2O2 Oxidation of benzene 15%
201
Co4O(C16H16N4)3 NHPI@MFU-1
Cyclohexene, ethylbenzene, cyclohexanol,
cyclohexane, atmospheric oxygen, N-
hydroxyphthalimide
Oxidation of hydrocarbons 2-95%
313
Cu(BPy)(H2O)2(BF4)2(BPy)
Cyclohexene and O2 Oxidation of cyclohexene 5-7%
314
VO(BDC) MOF-47 Cyclohexene, tert-butylhydroperoxide Oxidation of cyclohexene 55-90%
315,
316
Co(BPB) MFU-3 Cyclohexene and tert-butyl hydroperoxide Oxidation of cyclohexene 63%
74
MP11 Tb(TATB) MP-11@Tb-
mesoMOF 3,5-Di-tert-butylcatechol Oxidation of catechol 49%
317
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
Cu(BPED)2(H2O)2(SiF6)
Tetralin and tert-butyl hydroperoxide Oxidation of benzylic compounds 84-88%
318
Mn5Cl2(MnCl-
OCPP)(DMF)4(H2O)4 ZJU-18
Ethylbenzene, propylbenzene, tetralin,
diphenylmethane, fluorine, and 4-ethyl-1,1'-
biphenyl
Oxidation of Alkylbenzenes 18-99% 319
M3(BTC)2 (M = Cu, Co, Ni)
Hydroquinone and O2 Oxidation of hydroquinone
320
Cu3(BTC)2
Olive oil mill wastewaters Oxidation of polyphenol
321
Yb(OH)(2,6-AQDS)(H2O) Yb-RPF-5 Methylphenylsulfide Oxidation of sulfide >90%
322
Yb2(succinate)3
Methylsulfanylbenzene and H2O2 Oxidation of sulfides 50%
323
In4(OH)6(BDC)3
Methyphenylsulfide, (2-
ethylbutyl)phenylsulfide Oxidation of sulfide 100%
324
Na20(Ni8(ImDC)12)(H2O)28
CO, O2, and He Oxidation of CO
325
Zn4O(BDC)3-x(BDC-NH2)x
CO and O2 Oxidation of CO 80-90%
326
Au Zn(2Me-Im)2 Au@ZIF-8 CO and O2 Oxidation of CO 100%
327
Zr3O2(OH)2(BPDC)3-x(L7)x
Water and cerium ammonium nitrate Oxidation of water
328
[CuPW11O39H(Me4N)4]
[Cu3(BTC)2]4
PW12 MOF-
199 Thiols Aerobic oxidation of thiol 27-95%
329
Cu(PYMO)2
Tetralin Aerobic oxidation of olefin 52%
330
Co(PhIM)2
Tetralin Aerobic oxidation of olefin 23%
330
Au Zn4O(BDC)3 Au MOF-5 Benzyl alcohol, 1-phenylethanol, K2CO3 and
methanol Aerobic oxidation of alcohols 79-99%
331
Au Al(OH)(BDC) Au MIL-
53(Al)
Benzyl alcohol, 1-phenylethanol, K2CO3 and
methanol Aerobic oxidation of alcohols 56-98%
331
Co2(C6H12N2P2O6)2(H2O) STA-12(Co) (E)-Stilbene Aerobic epoxidation of (E)-stilbene 97%
332
Fe3O(H2O)3F(BTC)2 MIL-100(Fe) Thiophenol Aerobic oxidation of thiophenol >99%
311
ZnF(Am2TAZ)
Dibutylamine and acrylonitrile aza-Michael reaction 85%
217
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
Zn/Cu2(DDBD)(H2O)2 Zn/(S)-KUMOF-
1 3-Methyl citronellal carbonyl-ene reaction 89-92% 23-50% 284
Cu(PYMO)2
Benzyl azide and phenylacetylene 1,3-dipolar cycloaddition reactions >99%
233
[Cd3Cl6(L8)3]Ti(OiPr)4
1-Naphthaldehyde Alkylation of aldehyde >99% 94% 67
[Cd3(L8)4(NO3)6]
1-Naphthaldehyde Alkylation of aldehyde >99% 90% 334
Zn2(L9)(DMF)(H2O)Ti(OiPr)2
Diethylzinc, aromatic aldehydes Addition of diethylzinc to aromatic
aldehydes 99% 11-30% 209
Cu2(L10)(H2O)2(Ti(OiPr)2)n CMOF-3a Ethyl(phenylalkynyl)zinc, benzaldehyde Addition of diethylzinc to aromatic
aldehydes >99% 0% 176
Cu2(L11)(H2O)2(Ti(OiPr)2)n CMOF-3b Ethyl(phenylalkynyl)zinc, aromatic aldehydes Addition of alkylzinc to aromatic
aldehydes >99% 31-76% 176
Cu2(L12)(H2O)2(Ti(OiPr)2)n CMOF-4b Ethyl(phenylalkynyl)zinc, aromatic aldehydes Addition of alkylzinc to aromatic
aldehydes >99% 49-77% 176
Zn(HFIPBB) (R,S)-2-phenylpropionaldehyde, CCl4 Acetalization of (R,S)-2-
phenylpropionaldehyde 60% 30% 335
Sc2(C4O4)3
-Methyl benzeneacetaldehyde,
Benzaldehyde Acetalization of carbonyls 78-100%
276
Yb2(succinate)3
Benzaldehyde and trimethyl orthoformate acetalization of aldehydes 90%
323
Cu2(L13)2Cl2
Grignard reagent, cinnamaldehyde derivatives 1,2-addition of α,β-unsaturated
ketones 48-98% 51-99% 336
Pd(II) Zn4O(BDC)3 Pd(II) MOF-
5(Oh)
Diphenyliodoniumtetrafluoroborate,
nitrobenzene 64% 337
Zr3O2(OH)2(BDC-X)3
UiO-66-X (X =
NH2, Cl, Br,
NO2)
(+)-Citronellal Cyclization of citronellal 15-100%
338
Cu3(BTC)2
Citronellal Cyclization of citronellal >97%
71
Cu3(BTC)2
2-(1-Bromoethyl)-2-phenyl-1,3-dioxolane Rearrangement of the ethylene acetal of
2-bromopropiophenone 13-82%
338
Cu3(BTC)2
-Pinene oxide Isomerization of α-pinene oxide 54-86%
71
Zn2(TCPB)(Zn-DPFPP) ZnPO-MOF N-acetylimidazole and 3-pyridylcarbinol Intermolecular acyl-transfer reaction
339
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
Gd(R-L1H2)(R-L1H3)(H2O)4
trans-1,2-Diaminocyclohexane and 3-
methylbenzoyl chloride
Enantioselective separation of trans-
1,2-diaminocyclohexane 4-14% 273
Zn3O(D-PTT) D-POST-1 2,4-Dinitrophenyl acetate and ethanol Enantioselective transesterification
reaction 77% 8% 31
Zn4O(BDC-C6H5ON2)3
Ethyldecanoate Transesterification of ethyldecanoate 55%
217
PW11O40 Cr3O(H2O)2F(BDC)3 POM@MIL-
101(Cr) n-Butanol Esterification of alcohols 65%
340
PW12O40 Cu3(BTC)2 Keggin HPW/
Cu3(BTC)2 Acetic acid and 1-propanol Esterification of acetic acid 15-30%
341
Ag2(BPy)2(O3SCH2CH2SO3) (M =
Ag(I), Cu(I)) SLUG-21/22
2-Butanone, 2-pentanone, benzophenone, and
ethylene glycol Ketal Formation 31-97%
342
XM12O40 Cu3(BTC)2 (X = Si, Ge,
P, As; M = W, Mo) Ethyl acetate Ethyl acetate hydrolysis 63%
80
Fe2(DOT) Fe-MOF-74 Phenol and H2O2 Hydroxylation of phenol 5-60%
168
PW11O40 Cr3O(H2O)2F(BDC)3 POM@MIL-
101(Cr) Methanol Dehydration of methanol 75%
340
Pd Cr3O(H2O)2F(BDC)3 Pd/MIL-101 Propiophenone Reduction of aryl alkyl ketones 95-100%
343
Pd-Ni Cr3O(H2O)2F(BDC)3 Pd/Ni/MIL-101 Cyclohexanone, cycloheptanone, 3-heptanone Reduction of alkyl ketones 1-99%
344
Pd Zn4O(BDC)3 Pd/MOF-5 Styrene Hydrogenation of styrene >99.7%
159
Ru Zn4O(BDC)3 Ru/MOF-5 Benzene Hydrogenation of Benzene 25%
160
Pd(PYMO)2
1-Octene Hydrogenation of olefin 99%
290
Zn4O(BDC-C7H5ON-AuCl2)3 IRMOF-3-SI-Au 1,3-Butadiene Hydrogenation of 1,3-butadiene 97%
198
Ni Tb16(TATB)16 Ni-MesMOF-1 Styrene, H2, methanol Hydrogenation of styrene >99%
345
Ca(HFIPBB)(H2HFIPBB)0.5(H2O) AEPF-1 Styrene, H2, toluene Hydrogenation of styrene 100%
346
Pd Zn4O(BDC)3 Pd@MOF-5 Ethyl cinnamate Hydrogenation 100%
347
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
In2(OH)3(BDC)1.5
Nitrobenzene and 2-methyl-1-
nitronaphthalene Reduction of nitroaromatic 100%
324
Ni + Tb16(TATB)16 Ni-MesMOF-1 Nitrobenzene, NaBH4 Hydrogenolysis of nitrobenzene >99%
345
Yb(OH)(2,6-AQDS)(H2O) Yb-RPF-5 Thiophene Hydrosulfurization of thiophene >90%
322
Ni2(DOT)Mo(CO)6
Sibenzothiophene, indole, naphtalene,
dimethyldisulfide Hydrodesulfurization
348
VO(BDC-(Me)2) MOF-48 Methane, K2S2O8, trifluoroacetic acid Conversion of methane to acetic acid 36-48%
73
(Cu/ZnO) Zn4O(BDC)3 (Cu/ZnO)
MOF-5 CO/CO2/H2/He Methanol synthesis from CO/CO2/H2
349
Ni(BPy)(HBTC)
NH3BH3 H2 Generation 100%
350
Au-Pd ED-Cr3O(H2O)2F(BDC)3 Au-Pd/ED-MIL-
101 Formic acid Dehydrogenation of formic acid >99%
351
Cu(PYMO)2
Piperidine, benzonitrile, and butyraldehyde
Three-component coupling and
cyclization reactions for the synthesis
of propargylamines
55-99%
352
Cu(PYMO)2
Phenylacetylene, 2-aminopyridine, and
benzaldehyde
Three-component coupling and
cyclization reactions for the synthesis
of indoles
61-97%
352
Cu2(PDAI) PCN-124 Dimethoxymethylbenzene and malononitrile Sequential deacetalization-
Knoevenagel condensation reactions 100%
353
Al3O(H2O)2F(BDC-NH2)3 MIL-101(Al)-
NH2 2-methyl-2-phenyloxirane and malononitrile
Sequential Meinwald rearrangement–
Knoevenagel condensation reaction 80%
354
Cr3O(H2O)2(EDA)(BDC-SO3H)3 MIL-101(Cr)-
SO3H-NH2 benzaldehyde dimethyl acetal and CH3NO2
Sequential deacetalization-nitroaldol
reaction 97%
189
Pd + Cu3(BTC)2 Cu3(BTC)2(L14)
1.5(H2O)1.5
2-Iodobenzyl bromide, sodium azide,
ethynylbenzene
Sequential Sonogashira and click
reactions trace-100%
355
Zn4O(BDC-C7H5ON-AuCl2)3 IRMOF-3-SI-Au Ethynylaniline, octanal, and piperidine Three component coupling and
cyclization 95%
198
Zn4O(L15)3 CMOF-1 2-(tert-Butylsulfonyl)iodosylbenzene and 2,2-
dimethyl-2H-chromene derivatives
Sequential epoxidation and ring-
opening of epoxide 57-60% 50-81% 356
Chemical Formula Common
Name Substrate(s) Reaction(s) Catalyzed Conv. (%) ee (%) Ref.
Cu2(L13)2Cl2
Benzaldehyde, urea and ethyl acetoacetate Biginelli reaction 90% 0% 336
Zr3O2(OH)2(BPDC)3-x(L16)x
CO2, Xe light Photocatalytic CO2 reduction
328
Zr3O2(OH)2(BPDC)3-x(L17)x
2-(4-Methoxyphenyl)-1,2,3,4-
tetrahydroisoquinoline and MeNO2,
fluorescent light
Aza-Henry reactions 97%
328
Zr3O2(OH)2(BPDC)3-x(L17)x
p-Tolylmethanamine and MeCN, Xe light Photocatalytic aerobic amine coupling
Reactions 90%
328
Zr3O2(OH)2(BPDC)3-x(L17)x
Thioanisole, methanol, fluorescent light Aerobic photo-oxidation of thioanisole 73%
328
Zn2Sn(IV)(TPyP)(HCOO)2(H2O)4
Xe light Photo-oxygenation of 1,5-
dihydroxynaphthalene >99.8%
357
Zn2Sn(IV)(TPyP)(HCOO)2(H2O)4
Methyl(phenyl)sulfane Photo-oxygenation of Sulfides >99.9%
357
Mn2(L18)2(H2O)2
phenylmethanol and NaIO4, ambient light Oxidation of phenylmethanol 64%
358
Mn2(L19)(H2O)2
Phenylmethanol and NaIO4, ambient light Oxidation of phenylmethanol 97%
358
Pt Zr3O2(OH)2(L20)3
Water and Xe light Photocatlytic hydrogen evolution
83
Zr3O2(OH)2(BDC-NH2)3 UiO-66-NH2 Styrene derivatives and alcohols Photocatalitic aerobic oxygenation
359
Zn2(BDC)2(TED)
Styrene Radical polymerisation of styrene 71%
360
Zn2(BDC)2(TED)
Styrene Confinement of single polystyrene
chain 361
[{Ni-
(dmen)2}2{Fe(III)(CN)6}]PhBSO3 Pyrrole Oxidative polymerization of pyrrole
362
Nd(BTB)(H2O) MIL-103(Nd) Isoprene and modified methylaluminoxane Polymerization of isoprene 2 - >99%
363
Nd(BTC)(H2O) MIL-81(Nd) Isoprene and modified methylaluminoxane Polymerization of isoprene 2-77%
363
BPy = 4,4′-bipyridine, H4L1 = 2,2′-diethoxy-1,1′-binaphthalene-6,6′-bisphosphonic acid, BTC3-
= benzenetricarboxylate, BTT3-
= 1,3,5-
benzenetristetrazolate, H3PTA = tris-(4-carboxy-2-phenoxyethyl)amine, TATAB3-
= 4,4′,4″-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tribenzoate,
BTATB3-
= 4,4′,4″-(benzene-1,3,5-triyltris(azanediyl))tribenzoate, H2C4O4 = squaric acid, H4MDIP = methylenediisophthalic acid, 3,3′-TPDC2-
=
terphenyl-3,3′-dicarboxylate, DABCO = 1,4-diazabicyclo[2,2,2]octane, BTAPA = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide],
BDC2-
= benzenedicarboxylate, H4L2 = 5,5′-(anthracene-9,10-diyl)bis(benzene-1,3-diol), DDBD2-
= 2,2′-dihydroxy-6,6′-dimethyl(1,1′-biphenyl)-
4,4′-dicarboxylate, BTB3-
= 4,4′,4″-benzene-1,3,5-triyl-tribenzoate, L-IP = 1-(pyrrolidin-2-ylmethyl)-1H-imidazole, BPDC2-
=
biphenyldicarboxylate, H4L3 = 5,5′-(carbonylbis(azanediyl))diisophthalic acid, HPYMO = 2-hydroxypyrimidine, DETA = diethylenetriamine,
PBBM = 1,1′-(1,5-pentanediyl)bis-1H-benzimidazole, 5,5′-BDA2-
= 2,2′-dihydroxy-1,1′-binaphthalene-5,5′-dicarboxylate, asp- = aspartate, BPE =
1,2-bis(4-pyridyl)ethylene, H4TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, Mn(III)(salen) = (R,R)-(–)-1,2-cyclohexanediamino-N,N′-bis(3-
tert-butyl-5-(4-pyridyl)salicylidene)Mn(III)Cl, Mn(II)(salen) = (R,R)-(–)-1,2-cyclohexanediamino-N,N′-bis(3-tert-butyl-5-(4-
pyridyl)salicylidene)Mn(II), NDS2-
= naphthalene-disulfonate, NIC- = nicotinate, H4TpCPP = tetra(p-carboxyphenyl)porphyrin, H4-Co-DCDPD =
5,15-bis(3,5-dicarboxyphenyl)-10,20-bis(2,6-dibromophenyl)porphyrin, H2OBA = 4,4′-oxybis(benzoic acid), L4- = 2-(4-formylphenoxy)acetate,
H2-TMPyP = 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin, H3ImDC = 4,5-imidazoledicarboxylic acid, H4L5-Zn = meso-tetrakis(4-
carboxyphenyl)-porphyrinato zinc(II), L6-Mn = 5,15-dipyridyl-10,20-bis(pentafluorophenyl))porphyrinato manganese (III) chloride, acac =
acetylacentone, BTEC4-
= 1,2,4,5-benzenetetracarboxylate; 2,2′-BPy = 2,2′-bipyridine, H4TCPP = tetrakis(4-carboxyphenyl)porphyrin, SiMe2Fc =
1,1′-ferrocenediyl-dimethylsilane, H2BPB = 1,4-di(1H-pyrazol-4-yl)benzene, MP11 = Microperoxidase-11, TATB3-
= 4,4′,4″-s-triazine-2,4,6-
triyltribenzoate, BPED = meso-1,2-bis(4-pyridyl)-1,2-ethanediol, MnCl-H8OCPP = 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin
manganese(III) chloride, 2,6-AQDS2-
= anthraquinone-2,6-disulfonate, H3ImDC = 4,5-imidazoledicarboxylic acid, 2Me-Im- = 2-
methylimidazolate, H2L7 = chloro(η5-pentamethylcyclopentadienyl)(2-(4-carboxyl)phenyl-(5-carboxyl)pyridine-C
2,N′)iridium(III), PhIM
- =
phenylimidazolate, Am2TAZ- = diaminotriazolate, L8 = (R)-6,6′-dichloro-2,2′-dihydroxy-1,1′-binaphthyl-4,4′-bipyridine, L9
4- = (R)-2,2′-
dihydroxy-1,1′-binaphthyl-4,4′,6,6′-tetrabenzoate, H4L10 = (R)-2,2′-diethoxy-1,1′-binaphthyl-4,4′,6,6′-tetrakis(4-benzoic acid), H4L11 = (R)-2,2′-
dihydroxy-1,1′-dinaphthyl-4,4′,6,6′-tetrakis(4-benzoic acid), H4L12 = (R)-4,4′,4″,4‴ -(1E,1′E,1″E,1‴ E)-2,2′,2″,2‴ -(2,2′-dihydroxy-1,1′-
binaphthyl-4,4′,6,6′- tetrayl)tetrakis(ethene-2,1-diyl)tetrabenzoic acid, H2HFIPBB = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid), HL13 =
(S)-3-hydroxy-2-(pyridin-4-ylmethylamino)propanoic acid, DPFPP = 5,15-dipyridyl-10,20-bis(pentafluorophenyl))porphyrin, D-PTT- = (4S,5R)-
2,2-dimethyl-5-(1-(pyridin-4-ylamino)vinyl)-1,3-dioxolane-4-carboxylate, DOT4-
= 2,5-dioxidoterephthalate, ED = ethylenediamine, PDAI4-
=
5,5′-((pyridine-3,5-dicarbonyl)bis(azanediyl))-diisophthalate, EDA = Ethylenediamine, L14 = C5H4N-NH-Pd(Cl)2(PhCN), H2L15 = 4,4′-(1E,1′E)-
2,2′-(5,5′-(1E,1′E)-(1R,2R)-cyclohexane-1,2-diylbis(azan-1-yl-1-yli-dene)-bis(methan-1-yl-1-ylidene)bis(3-tert-butyl-4-hydroxy-5,1-
phenylene))bis(ethene-2,1-diyl)dibenzoic acid manganese(III) chloride, H2L16 = tris-carbonyl-chloro(5,5′-dicarboxyl-2,2′-bipyridine)rhenium(I),
H2L17 = [bis(2,2′-bipyridine,N1,N1′)(5,5′-dicarboxy-2,2′-bipyridine-)ruthenium(II)] dichloride, Sn(IV)TPyP = 5,10,15,20-tetra(4-pyridyl)-
tin(IV)porphyrin, L182-
= E-5-(2-(pyridin-4-yl)vinyl)isophthalate, L194-
= 5,5′-(3,4-diphenylcyclobutane-1,2-diyl)diisophthalate, H2L20 = bis(4-
phenyl-2-pyridine)(5,5′-di(4-carboxyl-phenyl)-2,2′-bipyridine)-iridium(III) chloride, TED = triethylenediamine, dmen = 1,1-
dimethylethylenediamine, PhBSO3- = p-phenylbenzenesulfonate.
Related Web Sites (accessed May 4, 2013)
1. BASF receives French Pierre Potier Award for metal organic frameworks (MOFs)
research: http://www.basf.com/group/pressrelease/P-12-408
2. EcoFuel world tour around the world with natural gas: http://www.ecofuel-world-tour.com/
3. Current technology of hydrogen storage:
http://www1.eere.energy.gov/hydrogenandfuelcells/storage/current_technology.html
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