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Supplementary Information ForThe Thermal Stability of Metal-Organic FrameworksColm Healy,1,2 Komal Patil,1,2 Benjamin H. Wilson,1,2 Lily Hermanspahn,1,2 Nathan C. Harvey-Reid,1,2 Ben I. Howard,1,2 Carline Kleinjan,1,2 James Kolien,1,2 Fabian Payet,2 Shane G. Telfer,3 Paul E. Kruger,1,2* Thomas D. Bennett4*Email Addresses: Tdb35@cam.ac.uk paul.kruger@canterbury.ac.nz 1 MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Physical and Chemical Sciences, University of Canterbury, Private Bag 4800, Christchurch, New Zealand2 School of Physical and Chemical Sciences, University of Canterbury, Private Bag 4800, Christchurch 8140, New Zealand3 MacDiarmid Institute for Advanced Materials and Nanotechnology, Institute of Fundamental Sciences, Massey University, Palmerston North, New Zealand4 Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, CB3 0FS, United KingdomContents:Page:List of Abbreviations2Supplementary Tables5Supplementary Figures42List of AbbreviationsAbbreviationLigand NameChemical FormulaABIm4-azabenzimidazolateC6H4N3?ADCAcetylenedicarboxylateC4O42?ADPC9,10-anthracenedi(4-phenylcarboxylate)C28H16O42?ADPC9,10-anthracenedi(4-phenylcarboxylate)C28H16O42?AZPY4,4′-azopyridineC10H8N4BDB4,4'-(1,3-Butadiyne-1,4-diyl)dibenzoateC18H8O42?BDCBenzene-1,4-dicarboxylateC8H4O42?BDPButene diphosphonateC4H8P2O64?BImbenzimidazolateC7H5N2?BPA1,2-Bis(4-pyridyl)ethene)C12H8N2BPB1,4-Bis(4-pyridyl)benzeneC16H12N2BPBP4,4'-Bis(4-pyridyl)biphenylC22H16N2BPD1,4-Bis(4-pyridyl)dureneC20H20N2BPDCBiphenyl dicarboxylateC14H8O42?BPE1,2-Bis(4-pyridyl)ethene)C12H10N2BPIN-(Pyidin-4-yl)isoniconamideC11H9N3OBPN4,4'-(2,6-Napthalene)-bipyC20H14N2BPNDIN,N′-di(4-pyridyl)-1,4,5,8-naphthalene diimideC24H12N4O4BPT4,7-bis(4-pyridyl)-1,1,3,3-tetramethylisoindolin-2-yloxylC23H23N2O·BPX1,4-bis(4-pyridyl)xyleneC18H16N2BPY4,4-bipyridineC10H8N2BPYDC2,2’-dipyridine-5,5’-dicarboxylic acidC12H6N2O42?BPYDC2,2’-dipyridine-5,5’-dicarboxylic acidC12H6N2O42?BPZ4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridineC10H14N4BQDPC1,4-benzoquinone-2,5-di(4-phenylcarboxyate)C20H10O62?BQDPC1,4-benzoquinone-2,5-di(4-phenylcarboxyate)C20H10O62?BRBIm5-bromobenzimidazolateC7H4N2Br?BTB1,3,5-Benzene TribenzoateC27H15O63-BTC1,3,5 - Benzene TricarboxylateC9H3O63?BTTCbenzo-tris-thiophene carboxylateC15H3O6S33?C2PYN-ethylpyridiniumC7H10N+C4MPYRN-butyl-N-methylpyrrolidiniumC9H20N+CAIm2-carboxaldehydeimidazolateC4H3N2O?CBIm5-chlorobenzimidazolateC7H4N2Cl?CDCCubane-1,4-dicarboxylateC10H6O42?CNIm4-cyanoimidazolateC4H2N3?DABCO1,4-diazabicyclo[2.2.2]octaneC6H12N2DBFN,N’-dibutylformamideC9H19NODCIm4,5-dichloroimidazolateC3HN2Cl2?DEFN,N’-diethylformamideC5H11NODMAdimethylammoniumC2H7N+DMFN,N’-dimethylformamideC3H7NODMBIm4,5-dimethylbenzimidazolateC9H9N2?DNDCDinapthyldicarboxylateC22H12O42?DNDCDinapthyldicarboxylateC22H12O42?DOBPDC4,4'-dioxido-3,3'-biphenyldicarboxylateC14H6O64?DOT2,5-Dioxidobenzene-1,4-dicarboxylate(Extended analogues are indicated by roman numerals, e.g. DOT-II)C8H2O64?EDB4,4'-(1,2-Ethynediyl)dibenzoateC16H8O42?EDPEthyenediphosphonateC2H4P2O64?EIm2-ethylimidazolateC5H7N2?TPPPtetra(4-phosphonophenyl)porphyrinC44H24N4O12P48?HMIm2-methoxyimidazolateC4H5N2O?HPDC4,5,9,10-Tetrahydropyrene-2,7-dicarboxylateC18H12O42?ImImidazolateC3H3N2?MBIm5-methylbenzimidazolateC8H7N2?MDPMethyenediphosphonateCH2P2O64?MIm2-methylimidazolateC4H5N2?MTPPAtetraphenylmethane tetrakis-4-phosphonic acidC25H32O12P4NBIm5-nitrobenzimidazolateC7H4N3O2?NDCNaphthalene-2,6-dicarboxylateC12H6O42?NIm2-nitroimidazolateC3H2NO3?NMPN-methyl-2-pyrrolidoneC5H9NONTBnitrilotrisbenzoateC21H12NO63?NTC1,4,5,8-napthalenetetracarboxylic acidC14H4O84?PBDC5-phosphonobenzene-1,3-dicarboxylic acidC8H7O7P2PDMPPiperazinedi(methylenephosphonate)C6H12N2P2O64?PrDPPropylenediphosphonateC3H6P2O64?PtDPPentanediphosphonateC5H10P2O64?PurPurinateC5H3N4?PYPZ3,3′,5,5′-tetramethyl-1H,1′H-4,4′-bipyrazoleC10H11N3PYZPyrazineC4H4N2PZDC3,5-PyrazoledicarboxylateC5H2N2O42?TATB4,4',4''-s-triazine-2,4-6- triyltribenzoateC24H12N3O63?TAZB3,3',5,5' - azobenzene tetracarboxylic acidC16H6N2O84?TDBB1,3,5-tris(3,5'-dicarboxy[1,1'-biphenyl]-4-yl)benzeneC48H24O126?TPDCTriphenyldicarboxylateC20H12O42?TPPAH1,3,5,7-tetrakis(4-phosphonophenyl)adamantineC31H36O12P4TPPMH3tetrakis[4-(dihyroxyphosphoryl)phenyl]methaneC25H24O12P45?VBPYDC2,2’-dipyridine-5,5’-divinylcarboxylic acidC16H10O42?Supplementary TablesSupplementary Table 1. Thermal decomposition data for the MOF-5 family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceNotesMOF-5[Zn4O(BDC)3]--4751MOF-5[Zn4O(BDC)3]--4002MOF-5[Zn4O(BDC)3]10Air4753MOF-5[Zn4O(BDC)3]5O24754MOF-5[Zn4O(BDC)3]10N25105MOF-5[Zn4O(BDC)3]--3506MOF-5[Zn4O(BDC)3]20N24507MOF-5[Zn4O(BDC)3]10N24008Cubic MOF-5(Zn4.28O12.8C24H11.3)10N25009Tetragonal MOF-5(Zn5.59O16.33C24H16.08)10N24509Ni-doped MOF-5[Zn4O(BDC)3]+ 42% Ni(0)--4002MOF-5 (Zn/Ni)[Zn3.48Ni0.52O(BDC)3]10N24805MOF-5 (Zn/Co)[Zn3.09Co0.91O(BDC)3]10N247510MOF-5 (Zn/Ni)[Zn3.64Ni0.36O(BDC)3]0.5N245011MOF-5 (Zn/Co)[Zn3.16Co0.84O(BDC)3]3Air44012MOF-5 (Zn/Co)[Zn3.68Co0.32O(BDC)3]3Air46212MOF-5(Be)[Be4O(BDC)3]0.2Ar5006IRMOF-61·2H2O[Zn4O(edb)3(H2O)2]--30013MOF-2[Zn2(BDC)2(H2O)2]--4001MOF-46[Zn(BDC(NH2))(DMF)]--350*15MOF-47[Zn2(BDC(CH3)4)2(DMF)0.5(H2O)1.5]--350*15IRMOF-6[Zn4O(BDC(C2H4))3]-N24001IRMOF-6[Zn4O(BDC(C2H4))3]--40016IRMOF-6[Zn4O(BDC(C2H4))3]5N240017MOF-5-allyloxy[Zn4O(BDC(CH2=CHCH2O)2)3]10N216018AIRMOF-3[Zn4O(BDC(NH2))3]--3751IRMOF-3[Zn4O(BDC(NH2))3]5N240017IRMOF-3-AM2 to AM-19[Zn4O(BDC(NH2))3-y(BDC(alkylamide))y]5N232519BMOF-5-dimethyl[Zn4O(BDC(CH3)2)3]10Air4253MOF-5-methyl[Zn4O(BDC(CH3))3]10Air4253LSK-11[Zn4O(BDC)2(BDC(PPh2))]10N250020IRMOF-3-BI-Pd[Zn4O(BDC(NH2))2.67(BDC(BI))0.03(BDC(BI)-PdOAc)0.30]-N225021DMTV-MOF-5-AB[Zn4O(BDC)1.92(BDC(NH2))1.08]5Air42522MTV-MOF-5-AC[Zn4O(BDC)1.86(BDC(Br))1.14]5Air35022MTV-MOF-5-AD[Zn4O(BDC)1.83(BDC(Cl)2)1.17]5Air30022MTV-MOF-5-AE[Zn4O(BDC)2.13(BDC(NO2))0.87]5Air30022MTV-MOF-5-AF[Zn4O(BDC)1.35(BDC(CH3)2)1.65]5Air42522MTV-MOF-5-AG[Zn4O(BDC)1.98(14ndc)1.02]5Air37522MTV-MOF-5-AH[Zn4O(BDC)2.04(BDC(CH2=CHCH2O)2)0.96]5Air20022MTV-MOF-5-AI[Zn4O(BDC)2.13(BDC(C7H7O)2)0.87]5Air22522MTV-MOF-5-EI[Zn4O(BDC(C7H7O)2)2.49(BDC(NO2))0.51]5Air22522MTV-MOF-5-AHI[Zn4O(BDC)1.52(BDC(CH2=CHCH2O)2)0.73(BDC(C7H7O)2)0.75]5Air20022MTV-MOF-5-EHI[Zn4O(BDC(NO2))1.19(BDC(CH2=CHCH2O)2)1.07(BDC(C7H7O)2)0.74]5Air20022MTV-MOF-5-ABCD[Zn4O(BDC)1.44(BDC(NH2))0.18(BDC(Br))0.81(BDC(Cl)2)0.57]5Air32522MTV-MOF-5-ACEF[Zn4O(BDC)1.29(BDC(Br))0.63(BDC(NO2))0.28(BDC(CH3)2)0.80]5Air30022MTV-MOF-5-ABCEFGHI[Zn4O(BDC)0.70(BDC(NH2))0.011(BDC(Br))0.39(BDC(NO2))0.21(BDC(CH3)2)0.46(14ndc)0.39(BDC(CH2=CHCH2O)2)0.35(BDC(C7H7O)2)0.39]5Air20022IRMOF-1-Dioxole[Zn4O(BDC(CH2O2))3]5N230023DIRMOF-1-Crownether1[Zn4O(BDC(12-crown-4))3]5N225024IRMOF-1-Crownether2[Zn4O(BDC(15-crown-5))3]5N225024IRMOF-1-thia-Crownether1[Zn4O(BDC(di-thia-12-crown-4))3]5N222524IRMOF-1-thia-Crownether2[Zn4O(BDC(tri-thia-15-crown-5))3]5N222524PCN-123[Zn4O(BDC(Azo))3]5N237525IRMOF-9[Zn4O(BPDC)3] Z = 25N242526IRMOF-9[Zn4O(BPDC)3]----37527IRMOF-9-UREA[Zn4O(BPDC-Urea)3]3N240028WUF-19[Zn4O(BPDC(CH2=CH))3]101:1 mixture of N2 and Air44029IRMOF-9-OH[Zn4O(BPDC(OH))3] Z=25N240031IRMOF-9-Methoxy[Zn4O(BPDC(OCH3))3]5N240031LSK-3[Zn4O(BPDC)2(BPDC(PPh2))]2N240032WUF-1[Zn4O(BPDC(dmcto))3]10N242533IRMOF-9-allyloxy[Zn4O(BPDC(CH2=CHCH2O))3]5 or 10N226034CIRMOF-10-NO2BnO[Zn4O(BPDC(NO2BnO))3]5N230031IRMOF-10-OH[Zn4O(BPDC(OH))3]5N235031IRMOF-10-Pro-Boc[Zn4O(S-BPDC(Pro-Boc))3]5N235035IRMOF-10-Pro[Zn4O(S-BPDC(Pro))3]5N235035CUB-5[Zn4O(cdc)3]5N2300*36IRMOF-61[Zn4O(edb)3]-N240014IRMOF-0Zn4O(adc)3(Et3N)6 Z = 2-N212037IRMOF-11[Zn4O(hpdc)3]--4001IRMOF-62[Zn4O(bdb)3]-N237514MOF-326[Zn4O(Et-PzDC)3]-N230014IRMOF-8[Zn4O(26ndc)3]10Air47538α-MUF-9[Zn4O(rac-BPDC(DA))3]Desolvated5N2-30[Zn4O(rac-BPDC(DA))3]Solv. = DBF5N237530[Zn4O(rac-BPDC(DA))3]Solv. = DBF5N239030PIP23-MUF-9[Zn4O(rac-BPDC(DA))3] Z=1.23, Desolvated5N240030β-MUF-9[Zn4O(rac-BPDC(DA))3] Z=2, Desolvated5N240030[Zn4O(rac-BPDC(DA))3] Z=2, Solv. = DEF5N240030[Zn4O(rac-BPDC(DA))3] Z=2, Solv. = DBF5N243030γ-MUF-9[Zn4O(rac-BPDC(DA))3]5N239030α-MUF-10[Zn4O(R or S-BPDC(DA))3]5N242530β-MUF-10[Zn4O(R or S-BPDC(DA))3] Z=25N245030γ-MUF-10[Zn4O(R or S-BPDC(DA))3]5N237530Notes:A) Claisen Rearrangement at 160 °C to reveal OH functionalities. 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Yaghi, Tetrahedron, 2008, 64, 8553-8557.38L. T. L. Nguyen, C. V. Nguyen, G. H. Dang, K. K. A. Le and N. T. S. Phan, J. Mol. Catal. A: Chem., 2011, 349, 28-35.Supplementary Table 2. Thermal decomposition data for the UiO-66 family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceNotesUiO-66Zr6O8H4(BDC)610O24001A?UiO-66Zr6O8H4(BDC)65N24252A?UiO-66Zr6O8H4(BDC)62O24253A?UiO-66Zr6O8H4(BDC)67N24504A?UiO-66Zr6O8H4(BDC)65N24505A?UiO-66Zr6O8H4(BDC)610O24756AEHU-30Zr6O8H4(BDC)65Air3757AUiO-66-(Nap)Zr6O8H4(1,4-NDC)610O23756AUiO-66-MeZr6O8H4(BDC-Me)62O23253BUiO-66-(Me)2Zr6O8H4(BDC-(Me)2)62O23253BUiO-66-(CF3)2Zr6O8H4(BDC-(CF3)2)62O23253BUiO-66-FZr6O8H4(BDC-F)65N24002BUiO-66-F4Zr6O8H4(BDC-(F)4)61.5Air3508BUiO-66-ClZr6O8H4(BDC-Cl)62O24003B?UiO-66-ClZr6O8H4(BDC-Cl)65N24252BUiO-66-BrZr6O8H4(BDC-Br)62O24003B?UiO-66-BrZr6O8H4(BDC-Br)65N24252BUiO-66-IZr6O8H4(BDC-I)65N23252BUiO-66-OHZr6O8H4(BDC-OH)67N2-4B?UiO-66-OHZr6O8H4(BDC-OH)610O23006BUiO-66-(OH)2Zr6O8H4(BDC-(OH)2)67N2-4B?UiO-66-(OH)2Zr6O8H4(BDC-(OH)2)62O22753BUiO-66-NH2Zr6O8H4(BDC-NH2)67N2-4B?UiO-66-NH2Zr6O8H4(BDC-NH2)610O23006B?UiO-66-NH2Zr6O8H4(BDC-NH2)62O23253B?UiO-66-NH2Zr6O8H4(BDC-NH2)6--3509BUiO-66-(NH2)2Zr6O8H4(BDC-(NH2)2)67N2-4BUiO-66-NO2Zr6O8H4(BDC-NO2)67N2-4B?UiO-66-NO2Zr6O8H4(BDC-NO2)62O22753B?UiO-66-NO2Zr6O8H4(BDC-NO2)610O23006B?UiO-66-NO2Zr6O8H4(BDC-NO2)61.5Air3258BUiO-67Zr6O8H4(BPDC)6530% O2/ N240010A?UiO-67Zr6O8H4(BPDC)610O24001A?UiO-67Zr6O8H4(BPDC)67N24504A?UiO-67Zr6O8H4(BPDC)65N24505A?UiO-67Zr6O8H4(BPDC)65Air50011AUiO-67-(Nap)2Zr6O8H4(DNDC)65Air42511AUiO-67-(Me)2Zr6O8H4(BPDC-(Me)2)65Air37511BPCN-700Zr6O16H16(BPDC-(Me)2)410N247512CUiO-67-F8Zr6O8H4(BPDC-F8)61.5Air3008BMOF-805Zr6O8H4(NDC-(OH)2)65Air-13BMOF-806Zr6O8H4(BPDC-(OH)2)65Air32513BUiO-67-NH2Zr6O8H4(BPDC-NH2)6530% O2/N235010BUiO-67-NH2Zr6O8H4(BPDC-NH2)67N24504CUiO-67-(NH2)2Zr6O8H4(BPDC-(NH2)2)6530% O2/N2-10C?UiO-67-(NH2)2Zr6O8H4(BPDC-(NH2)2)6--4009CUiO-67-(NO2)2Zr6O8H4(BPDC-(NO2)2)61.5Air3258BUiO-67-NO2Zr6O8H4(BPDC-NO2)67N2-4CUiO-67-ureaZr6O8H4(BPDC-N2H2CO)610Ar45014CUiO-67-bpyZr6O8H4(BPYDC)610N245015C?UiO-67-bpyZr6O8H4(BPYDC)610N250016CUiO-67-bpy-MeZr6O8H4(BPDC-Me)610N250015CUiO-67-vbpyZr6O8H4(VPBYDC)6-Air42517DUiO-67-(SMe)4Zr6O8H4(BPDC-(SMe)4)62N230018BUiO-67-SO2FZr6O8H4(BPDC-SO2F)6--35019CUiO-68-AnthraceneZr6O8H4(ADPDC)6--42520APCN-57Zr6O8H4(TPDC-(Me)4)610O23001CUiO-68-(OH)2Zr6O8H4(TPDC-(OH)2)65Air40021CUiO-68-(C=O)2Zr6O8H4(BQDPC)65Air40021CUiO-68-NH2Zr6O8H4(TPDC-NH2)65Air40022C?UiO-68-NH2Zr6O8H4(TPDC-NH2)610N245023C?UiO-68-NH2Zr6O8H4(TPDC-NH2)610N245024C"MOF-1"Zr6O8H4(TPDC-NC4O3H6)65Air40022C"MOF-2"Zr6O8H4(TPDC-NC4O3H4)65Air40022CSal-MOFZr6O8H4(TPDC-NC7OH6)65Air40025CUiO-68-(SH)2Zr6O8H4(TPDC-(SH)2)63N245026CUiO-68-AlkyneZr6O8H4(TPDC-C2H)65Air37527CUiO-68-Triazole1Zr6O8H4(TPDC-N3C3H4)65Air35027CUiO-68-Triazole2Zr6O8H4(TPDC-N3O2C5H6)65Air30027CUiO-68-Triazole3Zr6O8H4(TPDC-N3C8H6)65Air35027C"1"Zr6O8H4(TPDC-N2S)610Air35028CMOF-801Zr6O8H4(fumarate)65Air27513D?MOF-801Zr6O8H4(fumarate)65Air30029DZr-MuconateZr6O8H4(muconate)65O2-30DMOF-802Zr6O8H4(PZDC)65Air35013BDUT-67-ZrZr6O8H2(TDC)4(CH3COO)25Air30031BDUT-68-ZrZr6O8H2(TDC)4.5(CH3COO)1.55Air30031BDUT-69-ZrZr6O8H4(TDC)5(CH3COO)25Air30031BMOF-808Zr6O8H4(BTC)2(HCOO)65Air50013ANU-1000Zr6O16H16(TBAPy)210N250032ALMOFZr6O16H16(TCBPPy)25N250033AZr-CAU-24Zr6O16H16(TCPB)24Air40034ANotes:A) Unfunctionalised aromatic linkers.B) Aromatic linkers with functional groups (including CH3, CF3, OH, NH2, halides, etc.) in the ortho- position relative to the carboxylate functionalities. (Note : all functionalized derivatives of UiO-66 are in this category, as functional groups at any position on the BDC linker are positioned ortho- with respect to one carboxylate or the other).C) Aromatic linkers with functional groups (including CH3, CF3, OH, NH2, halides, etc.) in the meta- position relative to the carboxylate functionalities, or at a more remote position.D) Non-aromatic linkers.References:1R. C. Klet, Y. Liu, T. C. Wang, J. T. Hupp and O. K. Farha, J. Mater. Chem. A, 2016, 4, 1479-1485.2M. Kalaj, M. R. Momeni, K. C. Bentz, K. S. Barcus, J. M. Palomba, F. Paesani and S. M. Cohen, Chem. Commun., 2019, 55, 3481-3484.3D. Cunha, C. Gaudin, I. Colinet, P. Horcajada, G. Maurin and C. Serre, J. Mater. Chem. B, 2013, 1, 1101-1108.4M. J. Katz, Z. J. Brown, Y. J. Colon, P. W. Siu, K. A. Scheidt, R. Q. Snurr, J. T. Hupp and O. K. Farha, Chem. Commun., 2013, 49, 9449-9451.5J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130, 13850-13851.6R. Wei, C. A. Gaggioli, G. Li, T. Islamoglu, Z. Zhang, P. Yu, O. K. Farha, C. J. Cramer, L. Gagliardi, D. Yang and B. C. Gates, Chem. Mater., 2019, 31, 1655-1663.7M. Perfecto-Irigaray, G. Beobide, O. Castillo, I. da Silva, D. García-Lojo, A. Luque, A. Mendia and S. Pérez-Yá?ez, Chem. Commun., DOI:10.1039/C9CC00802K.8P. Ji, T. Drake, A. Murakami, P. Oliveres, J. H. Skone and W. Lin, J. Am. Chem. Soc., 2018, 140, 10553-10561.9R. Gil-San-Millan, E. Lopez-Maya, M. G. Hall, N. M. Padial, G. W. Peterson, J. B. DeCoste, L. M. Rodriguez-Albelo, J. E. Oltra, E. Barea and J. A. R. Navarro, ACS Appl. Mater. Interfaces, 2017, 9, 23967-23973.10C. Tian, J. Zhao, X. Ou, J. Wan, Y. Cai, Z. Lin, Z. Dang and B. Xing, Environ. Sci. Technol., 2018, 52, 3466-3475.11S. ?ien-?degaard, B. Bouchevreau, K. Hylland, L. Wu, R. Blom, C. Grande, U. Olsbye, M. Tilset and K. P. Lillerud, Inorg. Chem., 2016, 55, 1986-1991.12C.-X. Chen, C.-C. Cao, M. Pan, H.-P. Wang, J.-J. Jiang, Z.-W. 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Mater., 2015, 27, 6426-6431.22M. Carboni, Z. Lin, C. W. Abney, T. Zhang and W. Lin, Chem. Eur. J., 2014, 20, 14965-14970.23Y.-A. Li, S. Yang, Q.-K. Liu, G.-J. Chen, J.-P. Ma and Y.-B. Dong, Chem. Commun., 2016, 52, 6517-6520.24S. S. Nagarkar, A. V Desai, P. Samanta and S. K. Ghosh, Dalton Trans., 2015, 44, 15175-15180.25K. Manna, T. Zhang, M. Carboni, C. W. Abney and W. Lin, J. Am. Chem. Soc., 2014, 136, 13182-13185.26B. Gui, K.-K. Yee, Y.-L. Wong, S.-M. Yiu, M. Zeller, C. Wang and Z. Xu, Chem. Commun., 2015, 51, 6917-6920.27B. Li, B. Gui, G. Hu, D. Yuan and C. Wang, Inorg. Chem., 2015, 54, 5139-5141.28M. SK and S. Biswas, CrystEngComm, 2016, 18, 3104-3113.29G. Wi?mann, A. Schaate, S. Lilienthal, I. Bremer, A. M. Schneider and P. Behrens, Microporous Mesoporous Mater., 2012, 152, 64-70.30V. Guillerm, S. Gross, C. Serre, T. Devic, M. Bauer and G. Ferey, Chem. Commun., 2010, 46, 767-769.31V. Bon, I. Senkovska, I. A. Baburin and S. Kaskel, Cryst. Growth Des., 2013, 13, 1231-1237.32P. Deria, W. Bury, J. T. Hupp and O. K. Farha, Chem. Commun., 2014, 50, 1965-1968.33R. Zou, X. Ren, F. Huang, Y. Zhao, J. Liu, X. Jing, F. Liao, Y. Wang, J. Lin, R. Zou and J. Sun, J. Mater. Chem. A, 2015, 3, 23493-23500.34M. Lammert, H. Reinsch, C. A. Murray, M. T. Wharmby, H. Terraschke and N. Stock, Dalton Trans., 2016, 45, 18822-18826.Supplementary Table 3. Thermal decomposition data for s-block carboxylate MOFs.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceULMOF-1Li2(2,6-NDC)10N26101UL-MOF-2Li2(BPDC)10N2Air5755202-Li2(BDC)10Air5203UL-MOF-3Li2(C16H4O6S)10N2Air5005002Be12(OH)12(BTB)42N25004MIL-123(Mg)Mg12(H2O)12(μ2-H2O)6)(BTB)8(dioxane)6)·11 dioxane1O24005[H2N(CH3)2][Ca7(BTB)5(H2O)8(DMF)4]?4H2O10N25256[H2N(CH3)2]2[Sr5(BTB)4(H2O)6]10N25256[H2N(CH3)2][Ba(BTB)(H2O)]10N25006Mg3(BDC)3(DMA)410N25757Mg3(BDC)3(EtOH)210N25757Mg3(BPDC)3(DMA)410N25507Li(NDC-H)(H2O)2-N22508Na2(NDC)(DMF)-N24758Mg2(NDC)2(H2O)3-N25008Ca(NDC)(DMF)-N25008Sr(NDC)(DMF)-N25258References:1D. Banerjee, S. J. Kim and J. B. Parise, Cryst. Growth Des., 2009, 9, 2500-2503.2D. Banerjee, L. A. Borowski, S. J. Kim and J. B. Parise, Cryst. Growth Des., 2009, 9, 4922-4926.3Y.-Y. Liu, J. Zhang, L.-X. Sun, F. Xu, W.-S. You and Z. Yi, Inorg. Chem. Commun., 2008, 11, 396-399.4K. Sumida, M. R. Hill, S. Horike, A. Dailly and J. R. Long, J. Am. Chem. Soc., 2009, 131, 15120-15121.5C. Volkringer, T. Loiseau, J. Marrot and G. Férey, CrystEngComm, 2009, 11, 58-60.6K. S. Asha, M. Makkitaya, A. Sirohi, L. Yadav, G. Sheet and S. Mandal, CrystEngComm, 2016, 18, 1046-1053.7R. P. Davies, R. J. Less, P. D. Lickiss and A. J. P. White, Dalton Transactions, 2007, DOI: 10.1039/B705028C, 2528-2535.8D. S. Raja, J.-H. Luo, C.-T. Yeh, Y.-C. Jiang, K.-F. Hsu and C.-H. Lin, CrystEngComm, 2014, 16, 1985-1994.Supplementary Table 4. Thermal decomposition data for the HKUST-1 family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceHKUST-1Cu3(BTC)210-27515N22751020Ar27511ZnHKUST-1Zn3(BTC)2-Air3252Mo3(BTC)21-3253Ni3(BTC)2(Me2NH)2(H2O)1-3253Ru3(BTC)21-4003UHM-31Cu3(F-BTC)25Ar2604Cu3(NO2-BTC)2-N22805Cu3(CONCH3-BTC)2-N22805Cu3(Br-BTC)2-N23005Cu3(Me-BTC)25N23256Cu3(Et-BTC)25N23256Cu3(MeOBTC)2-N22755PCN-6Cu3(TATB)2(H2O)310-3007PCN-6Cu3(TATB)2(H2O)3--2508PCN-6’Cu6(H2O)6(TATB)4·DMA·12H2O--2758NOTT-112Cu3(TDBB)22N23509PCN-6-NO2Cu3(TATB)210-2507References:1K.-S. Lin, A. K. Adhikari, C.-N. Ku, C.-L. Chiang and H. Kuo, Int. J. Hydrogen Energy, 2012, 37, 13865-13871.2M. K. Bhunia, J. T. Hughes, J. C. Fettinger and A. Navrotsky, Langmuir, 2013, 29, 8140-8145.3C. R. Wade and M. Dinc?, Dalt. Trans., 2012, 41, 7931-7938.4K. Peikert, F. Hoffmann and M. Fr?ba, CrystEngComm, 2015, 17, 353-360.5Y. Cai, A. R. Kulkarni, Y.-G. Huang, D. S. Sholl and K. S. Walton, Cryst. Growth Des., 2014, 14, 6122-6128.6Y. Cai, Y. Zhang, Y.-G. Huang, S. R. Marder and K. S. Walton, Cryst. Growth Des., 2012, 12, 3709-3713.7E. Mühlbauer, A. Klinkebiel, O. Beyer, F. Auras, S. Wuttke, U. Lüning and T. Bein, Microporous Mesoporous Mater., 2015, 216, 51-55.8S. Ma, D. Sun, M. Ambrogio, J. A. Fillinger, S. Parkin and H.-C. Zhou, J. Am. Chem. Soc., 2007, 129, 1858-1859.9Y. Yan, X. Lin, S. Yang, A. J. Blake, A. Sailly, N. R. Champness, P. Hubberstey and M. Schr?der, Chem. Commun., 2009, 1025-1027.10D. Mustafa, E. Breynaert, S. R. Bajpe, J. A. Martens, C. E. A. Kirschhock, Chem. Commun., 2011, 47, 8037-8039.11S. Abednatanzi, A. Abbasi, M. Masteri-Farahani, New J. Chem., 2015, 39, 5322-5328.Supplementary Table 5. Thermal decomposition data for the MIL-101 family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceNotesMIL-100Fe3(BTC)3O22501Cr3(BTC)2O22502Al3(BTC)3O24003Fe3(BTC)10N23004MIL-101Cr3(1,4-BDC)2O22755Cr3(1,4-BDC)(Keggin)2O23255AMIL-96Ga3(BTC)--4006BAl3(BTC)2O23507Al3(BTC)10N22754In3(BTC)2O22508MIL-102Cr3(NTC)2O22259PCN-332Al3(BTTC)2N235010Fe3(BTTC)2N232510Sc3(BTTC)2N240010V3(BTTC)2N210010In3(BTTC)2N227510PCN-333Al3(TATB)2N242510Fe3(TATB)2N237510Sc3(TATB)2N245010MIL-127Fe3(TAZB)2O227511Fe3(TAZB)3O230012Fe2Mg(TAZB)3O230012CFe2Co(TAZB)3O230012CFe2Ni(TAZB)3O230012CNotes:A = Contains monolacunary phosphotungstate Keggin anions within MIL-101’s poresB = Heating rate and atmosphere not statedC = Mixed metal systems References:P. Horcajada, S. Surble, C. Serre, D.-Y. Hong, Y.-K. Seo, J.-S. Chang, J.-M. Greneche, I. Margiolaki and G. Ferey, Chem. Commun. (Cambridge, U. K.), 2007, 2820-2822G. Ferey, C. Serre, C. Mellot-Draznieks, F. Millange, S. Surble, J. Dutour and I. Margiolaki, Angew. Chem., Int. Ed., 2004, 43, 6296-6301C. Volkringer, D. Popov, T. Loiseau, G. Ferey, M. Burghammer, C. Riekel, M. Haouas and F. Taulelle, Chem. Mater., 2009, 21, 5695-5697V. Gargiulo, M. Alfe, F. Raganati, L. Lisi, R. Chirone and P. Ammendola, Fuel, 2018, 222, 319-326G. Ferey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surble and I. Margiolaki, Science (Washington, DC, U. S.), 2005, 309, 2040-2042C. Volkringer, T. Loiseau, G. Ferey, C. M. Morais, F. Taulelle, V. Montouillout and D. Massiot, Microporous Mesoporous Mater., 2007, 105, 111-117.T. Loiseau, L. Lecroq, C. Volkringer, J. Marrot, G. Ferey, M. Haouas, F. Taulelle, S. Bourrelly, P. L. Llewellyn and M. Latroche, J. Am. Chem. Soc., 2006, 128, 10223-10230.C. Volkringer and T. Loiseau, Mater. Res. Bull., 2006, 41, 948-954.S. Surble, F. Millange, C. Serre, T. Dueren, M. Latroche, S. Bourrelly, P. L. Llewellyn and G. Ferey, J. Am. Chem. Soc., 2006, 128, 14889-14896.D. Feng, T.-F. Liu, J. Su, M. Bosch, Z. Wei, W. Wan, D. Yuan, Y.-P. Chen, X. Wang, K. Wang, X. Lian, Z.-Y. Gu, J. Park, X. Zou and H.-C. Zhou, Nat. Commun., 2015, 6, 5979/5971-5979/5978.A. Dhakshinamoorthy, M. Alvaro, H. Chevreau, P. Horcajada, T. Devic, C. Serre and H. Garcia, Catal. Sci. Technol., 2012, 2, 324-330.S. Wongsakulphasatch, F. Nouar, J. Rodriguez, L. Scott, C. Le Guillouzer, T. Devic, P. Horcajada, J. M. Greneche, P. L. Llewellyn, A. Vimont, G. Clet, M. Daturi and C. Serre, Chem. Commun. (Cambridge, U. K.), 2015, 51, 10194-10197.Supplementary Table 6. Thermal decomposition data for the MOF-74 family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceMOF-74[Mg2(dot)(Solvent)2]--3751MOF-74[Mg2(dot)(Solvent)2]20Air5262MOF-74[Mg2(dot)(Solvent)2]2Air4003MOF-74[Mg2(dot)(Solvent)2]2N25203Zn-MOF-74[Zn2(dot)(Solvent)2] 20Air4084Zn-MOF-74[Zn2(dot)(Solvent)2] 20Air3972Zn-MOF-74[Zn2(dot)(Solvent)2] 2Air2803Zn-MOF-74[Zn2(dot)(Solvent)2] 2N24403Cd-MOF-74[Cd2(dot)(Solvent)2]20Air3504Co-MOF-74[Co2(dot)(Solvent)2]-Air2343,5Co-MOF-74[Co2(dot)(Solvent)2]2Air2203Co-MOF-74[Co2(dot)(Solvent)2]20Air3312Co-MOF-74[Co2(dot)(Solvent)2]-N23205Co-MOF-74[Co2(dot)(Solvent)2]2N24603Mn-MOF-74[Mn2(dot)(Solvent)2]2Air2603Mn-MOF-74[Mn2(dot)(Solvent)2]20Air3072Mn-MOF-74[Mn2(dot)(Solvent)2]2N24603Ni-MOF-74[Ni2(dot)(Solvent)2] 10Air2506Ni-MOF-74[Ni2(dot)(Solvent)2] 20Air3462Ni-MOF-74[Ni2(dot)(Solvent)2] 2Air2203Ni-MOF-74[Ni2(dot)(Solvent)2] 2N23403IRMOF-74-II[Mg2(dot-II)(Solvent)2] 5Air3508IRMOF-74-III[Mg2(dot-III)(Solvent)2] 5Air2758IRMOF-74-IV[Mg2(dot-IV)(Solvent)2] 5Air2008IRMOF-74-V[Mg2(dot-V)(Solvent)2] 5Air2758IRMOF-74-V-hex[Mg2(dot-V-hex)(Solvent)2] 5Air2258Zn-IRMOF-74-VI[Zn2(dot-VI)(Solvent)2] 5Air2508IRMOF-74-VII[Mg2(dot-VII)(Solvent)2] 5Air3008IRMOF-74-VII-oeg[Mg2(dot-VII-oeg)(Solvent)2] 5Air2258IRMOF-74-IX[Mg2(dot-IX)(Solvent)2] 5Air3008IRMOF-74-XI[Mg2(dot-XI)(Solvent)2] 5Air2258M2M-MOF-74[Mg0.428Co1.572(dot)(Solvent)2]5Air2509M4M-MOF-74[Mg0.190Co0.612Ni0.562Zn0.636(dot)(Solvent)2]5Air3259M6M-MOF-74[Mg0.124Sr0.004Mn0.212Co0.592Ni0.528Zn0.540(dot)(Solvent)2]5Air3009M8M-MOF-74[Mg0.268Ca0.034Sr0.048Mn0.258Fe0.314Co0.432Ni0.392Zn0.254(dot)(Solvent)2]5Air3009M10M-MOF-74[Mg0.269Ca0.022Sr0.030Ba0.075Mn0.234Fe0.422Co0.272Ni0.282Zn0.199Cd0.196(dot)(Solvent)2]5Air3009Ni-IRMOF-74-II[Ni2(dot-II)(Solvent)2] 10Air2506Ni-IRMOF-74-III[Ni2(dot-III)(Solvent)2] 10Air2506Ni-IRMOF-74-IV[Ni2(dot-IV)(Solvent)2] 10Air2756Ni-IRMOF-74-V[Ni2(dot-V)(Solvent)2] 10Air2506References:1A. R. Millward and O. M. Yaghi, J. Am. Chem. Soc., 2005, 127, 17998-17999.2M. Díaz-García, ?. Mayoral, I. Díaz and M. Sánchez-Sánchez, Cryst. Growth Des., 2014, 14, 2479-2487.3S. A. FitzGerald, B. Burkholder, M. Friedman, J. B. Hopkins, C. J. Pierce, J. M. Schloss, B. Thompson and J. L. C. Rowsell, J. Am. Chem. Soc., 2011, 133, 20310-20318.4M. Díaz-García and M. Sánchez-Sánchez, Microporous Mesoporous Mater., 2014, 190, 248-254.5P. D. C. Dietzel, Y. Morita, R. Blom and H. Fjellv?g, Angew. Chem, Int. Ed., 2005, 44, 6354-6358.6S. Peng, B. Bie, Y. Sun, M. Liu, H. Cong, W. Zhou, Y. Xia, H. Tang, H. Deng and X. Zhou, Nat. Commun., 2018, 9, 1293.7T. M. McDonald, W. R. Lee, J. A. Mason, B. M. Wiers, C. S. Hong and J. R. Long, J. Am. Chem. Soc., 2012, 134, 7056-7065.8H. Deng, S. Grunder, K. E. Cordova, C. Valente, H. Furukawa, M. Hmadeh, F. Gándara, A. C. Whalley, Z. Liu, S. Asahina, H. Kazumori, M. O’Keeffe, O. Terasaki, J. F. Stoddart and O. M. Yaghi, Science, 2012, 336, 1018-1023.9L. J. Wang, H. Deng, H. Furukawa, F. Gándara, K. E. Cordova, D. Peri and O. M. Yaghi, Inorg. Chem., 2014, 53, 5881-5883.Supplementary Table 7. Thermal decomposition data for the Pyrazolate family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)Reference-[Zn(BPZ)]5 to 10N24751-[Co(BPZ)]5 to 10N24001-[Cd(BPZ)(μ-DMF)]5 to 10N21751-[Cu(BPZ)(μ-MeCN)]5 to 10N22501-[Ni(BPZ)]5 to 10N23501CFA-10[Fe(BPZ)]-N23502-α-[Ag2(BPZ)]-N24003-α-[Cu2(BPZ)]-N25003-β-[Ag2(BPZ)]-N24003-β-[Cu2(BPZ)]-N25003-[Cu2(TMP)]10N23004CFA-2[Cu2(PhBPZ)]10N26005CFA-3[Ag2(PhBPZ)]10N24005CFA-9[Cu2(PhBPZ)]10N24506CFA-9[Cu2(PhBPZ)]10O23506Fe-CFA-6[Fe(μ-OH)(BPZ)]10N24007Ga-CFA-6[Ga(μ-OH)(BPZ)]10N24207-[Zn(NO2-BPZ)]5 to 10N23908-[Co(NO2-BPZ)]5 to 10N23408-[Zn(DMP)]5 to 10N25209-[Co(DMP)]5 to 10N23409-[Zn(TMP)]10N240010-[Co(TMP]10N242510-[Co(BDPB)]8N250011-[Cd(BDPB)]8N250011-[Zn(BDPB)]8N250011-[Zn(BDPP)]8N237511-[Co(BDPP)]8N230011-[Cd(BDPP)]8N240011MFU-2[Co(BDPB)]10N240012MFU-1[Co4O(BDPB)6]10N234013CFA-12[Co(NO2-BDPB)]10N230014-[Fe2(BDP)3]-Air28015-[Co(BDP)]1N245016-[Co(BDP)]10O229017-[Zn(BDP)]1N240018-[Zn(1,3-BDP)]1N250018-[Ni(BDP)]10N246019-[Ni(NH2-BDP)]10N250020-[Ni(OH-BDP)]10N245020-[Ni(NO2-BDP)]10N240020-[Ni(SO3H-BDP)]10N245020-[Zn(NH2-BDP)]10N250020-[Zn(OH-BDP)]10N245020-[Zn(NO2-BDP)]10N240020-[Ni8(OH)4(H2O)2(BDP)6]20Air38021-[Ni8(OH)4(H2O)2(DABP)6]20Air35021-[Ni8(OH)4(H2O)2(BDAP)6]20Air35021-[Ni8(OH)4(H2O)2(Me-BDAP)6]20Air32521-[Ni8(OH)4(H2O)2(CF3-BDAP)6]20Air37521-[Ni8(OH)4(H2O)2(TET)6]10N240022Cu(I)[CFA-4]Cu[Cu5(TFPB)3]10N240023K[CFA-4]K[Cu5(TFPB)3]10N240023-[Ni3(BTP)2]3N240024-[Cu3(BTP)2]3N237524-[Zn3(BTP)2]3N245024-[Ni3(BTPP)2]7N245025-[CuI2CuII(OH)(BTPP)]7N232525References:1.Pettinari, C.; T?b?caru, A.; Boldog, I.; Domasevitch, K. 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CrystEngComm 2015, 17 (27), 4992-5001.Supplementary Table 8. Thermal decomposition data for the ZIF family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceTopologyNotesZIF-1Zn(Im)25N25251crbAZIF-3Zn(Im)210N24502dftAZIF-4Zn2(Im)410N23752cagAZIF-4Zn2(Im)410Ar6003cagAZIF-4(Co)Co(Im)210Ar5502cagBZIF-4-Co zniCo(Im)25N25004zniBIF-1-LiLiB(Im)45N24255zniZIF-8Zn(MIm)25N25756sodZIF-8Zn(MIm)25N24257sodZIF-8Zn(MIm)22Air3008sodZIF-67(Co-ZIF-8)Co(MIm)210N23009sodZIF-67(Co-ZIF-8)Co(MIm)25N23757sodZIF-67(Co-ZIF-8)Co(MIm)22Air28010sodCdIF-1Cd(MIm)25N23507sodCdIF-1Cd(MIm)22Air30010sodBIF-3-LiLiB(MIm)4. (solvent)x5N23005sodBIF-3-CuCuB(MIm)4 (solvent)x5N23005sodZIF-65Zn(NIm)25N230011sodZIF-65Zn(NIm)25Air34012sodZIF-65(Co)Co(NIm)25Air20012sodZIF-7Zn(BIm)25N247513sodZIF-7Zn(BIm)22Air47510sodZIF-9Co(BIm)210N247514sodZIF-9Co(BIm)25N250013sodZIF-11Zn(BIm)25N25001rhoZIF-11Zn(BIm)22Air47510rhoZIF-12Co(BIm)25N252513rhoCdIF-13Cd(BIm)21.5N240015sodBIF-40CuBH(BIm)310N240016*ZIF-21Co(Pur)25N230017ltaZIF-20Zn(Pur)25N235017ltaNotes:A) Compounds undergo solid state amorphization at ca 300 °C, before recrystallization to ZIF-zni, which then itself melts.B) Compound amorphizes at ca 300 °C, and subsequently recrystallizes to a dense framework at 300 °C.References:1K. S. Park, Z. Ni, A. P. C?té, J. Y. Choi, R. Huang, F. J. Uribe-Romo, H. K. Chae, M. O’Keeffe and O. M. Yaghi, Proc. Natl. Acad. Sci. U. S. A., 2006, 103, 10186-10191.2T. D. Bennett, D. A. Keen, J.-C. Tan, E. R. Barney, A. L. Goodwin and A. K. Cheetham, Angew. Chemie Int. Ed., 2011, 50, 3067-3071.3T. D. Bennett, J.-C. Tan, Y. Yue, E. 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Thermal decomposition data for the Hybrid Ultramicroporous (HUM) family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceSIFSIX-1-Cu[Cu(bpy)2(SiF6)]n5N21501TIFSIX-1-Cu[Cu(bpy)2(TiF6)]n10O21502SIFSIX-2-Cu-i[Cu(bpa)2(SiF6)]n10N21703,4,5.TIFSIX-2-Cu-i[Cu(bpa)2(TiF6)]n10N22604,6TIFSIX-2-Ni-i[Ni(bpa)2(TiF6)]n10N22706GeFSIX-2-Cu-i[Cu(bpa)2(GeF6)]n10N22107SIFSIX-3-Zn[Zn(pyz)2(SiF6)]n20He1503,8SIFISX-3-Cu[Cu(pyz)2(SiF6 )]n--1505SIFSIX-3-Ni[Ni(pyz)2(SiF6 )]n20N22259,10,11TIFSIX-3-Ni[Ni(pyz)2(TiF6)]n20N228011TIFSIX-4-Cu-i[Cu(bpb)2(TiF6)]n20N225012SIFSIX-5 Zn-i[Zn(bpbp)2(SiF6)]n-N230013SIFSIX-6-Zn-i[Zn(bpn)2(SiF6)]n-N230013SIFSIX-7-Cu[Cu(bpe)2(SiF6)]n20-20014SIFSIX-8-Cu[Cu(bpi)2(SiF6)]n3N220015SIFSIX-12-Cu[Cu(bpt)2(SiF6)]n5N220016SIFSIX-13-Zn[Zn(bpndi)2(SiF6)]n10N235017SIFSIX-14-Cu-i[Cu(azpy)2(SiF6)]n5N217018,19TIFSIX-14-Cu-i[Cu(azpy)2(TiF6)]n10N225020,21GEFSIX-14-Cu-i[Cu(azpy)2(GeF6)]n10N225021SIFSIX-17-Cu[Cu(pyz-NH2)2(SiF6)]n5N221022DICRO-2-Ni[Ni(bpa)2(Cr2O7)]n10N220023DICRO-3-Co-i[Co(azpy)2(Cr2O7)]n10N222524DICRO-3-Cu-i[Cu(azpy)2(Cr2O7)]n10N220024DICRO-3-Ni-i[Ni(azpy)2(Cr2O7)]n10N227524DICRO-3-Zn-i[Zn(azpy)2(Cr2O7)]n10N222524DICRO-4-Ni-i[Ni(bpb)2(Cr2O7)]n10N227525DICRO-5-Co-i[Co(bpx)2(Cr2O7)]n10N227526DICRO-5-Ni-i[Ni(bpx)2(Cr2O7)]n10N228026DICRO-6-Co-i[Co(bpd)2(Cr2O7)]n10N225026DICRO-6-Ni-i[Ni(bpd)2(Cr2O7)]n10N225026DICRO-7-Cu[Cu(pypz)2(Cr2O7)]n10N220027DICRO-8-Cu[Cu(bpz)2(Cr2O7)]n10N222527NbOFFIVE-1-Ni[Ni(pyz)2(NbOF5)]n20N232528NbOFFIVE-2-Cu-i[Cu(bpa)2(NbOF5)]n20N225029NbOFFIVE-2-Ni-i[Ni(bpa)2(NbOF5)]n10N228530ALFFIVE-1-Ni[Ni(pyz)2(AlF5(H2O))]n5N226031FEFFIVE-1-Ni[Ni(pyz)2(FeF5(H2O))]n5N223031References:S. 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Thermal decomposition data for the phosphonate family of materials.NameCompositionHeating Rate (°C/min)AtmosphereTd (°C)ReferenceNotesVSB-2Ni4(MDP)2·(H2O)35O22755AVSB-3(Zn)Zn2(MDP)·(H2O) 5O22509BVSB-4(Zn)Zn2(MDP)5O26009MIL-48NaZn2(OH)(MDP)·1.5H2O5O22009MIL-48calcNaZn2(OH)(MDP)5O24009IIAl(H2O)(EDP)10-5508IIIGa(H2O)(EDP)10-5408MIL-57Zr(MDP)--75010CIFe(H2O)(EDP)10-4258III(C5H14N2)Zn4(EDP-H2)(EDP)230N24257I-Li(C5H14N2)Zn2(PrDP-H)2·Li15N25257Al2(EDP)(H2O)2F2·H2O--375141Cu2(EDP)(H2O)210N230032Cu2(PrDP)(H2O)310N222533Zn2(EDP)(H2O)210N227534Zn2(PrDP)10N25003Al2(PrDP)(H2O)2F2·H2O5N247511I(C5H14N2)Zn2(PrDP-H)215N23507II(C5H14N2)Zn4(BDP-H2)(BDP)220N242573Cu(H2O)2(BDP-H2)--200154Zn(BDP-H2)·2H2O--25015Ga4(PtDP)3(C5H5N)210N245016D1Cu3[NH2(CH2PO3)2]210O230013E2Co3[NH2(CH2PO3)2]210O2300133Mn[HN2(CH2PO3H)2]2(H2O)210O230013Ni-STA-12Ni2(PDMP)·8H2O5Air40012Ni2L[Ni2(H2O)2L]·5.4H2O5N240017Co2L[Co2(H2O)2L]·5.4H2O5N240017Fe2L[Fe2(H2O)2L]·5.4H2O5N238017Ni2L’[Ni2(H2O)2L’]·5.8H2O5N245017Co2L’Co4L’1.5(CH3CO2)1.5(OH,H2O)3]·(NH4)0.5(H2O)5.55N238017STA-12(Mg)Mg2(PDMP)·xH2O2.5Dry air32518STA-12(Mn)Mn2(PDMP)·xH2O2.5Dry air25018STA-12(Fe)Fe2(PDMP)·xH2O2.5Dry air12518STA-12(Co)Co2(PDMP)·xH2O2.5Dry air27518STA-12(Ni)Ni2(PDMP)·xH2O2.5Dry air32518STA-16(Co)Co2[(H2O)2(C12H22N2P2O6)] ·11H2O1.5Air22519MIL-91(Al)Al(OH)(HO3PCH2NC4H10NCH2PO3H)·nH2O (n ～ 3)-O22759MIL-91-TiTiO(O3PCH2NHC4H10NHCH2PO3)·nH2O (n ～ 3.6)-O22009PCMOF-3Zn3(C6H9O9P3)(H2O)2 · 2H2O5N245021PCMOF-10Mg2(H2O)4(H2L)·H2O2…20022Cu5[(O3P)2C6H3CO2]2(H2O)63N225023Cd2(pBDC)(H2O)310Air47524PCMOF20(DMA)3[Zr(HL)F2](H2O)82N222525CAU-14[Cu3(PPT)(H2O)3]·10H2O4Air37526CuBDPEtCu(C10H16O6P2)5N235027CuBDPMeCu(C6H8O6P2)5N23502713α[Co4L3(μ3-OH)(H2O)3](SO4)0.5·xH2O--325281’3α[Co4L3(μ3-OH)(H2O)3](SO4)0.5·xH2O--32528Al2[O3PC6H4PO3](H2O)2F2·2H2O5N222529F2Ga2[O3PCH2(C6H4)CH2PO3](H2O)2F25N220030G3Ga2{[O3PCH2(C6H4)CH2PO3]1-x(HPO3)2x} (H2O)2F2(0 ≤ x ≤ 0.146) x ) 0.5415N220030G4Ga2{[O3PCH2(C6H4)CH2PO3]0.853(6)(HPO3)0.29(1)}(H2O)2F25N220030GNi-CAU-29Ni-Ni-H8TPPP4Air40034Ni-CAU-29Ni-Ni-H8TPPP4N240034Mn-CAU-29Mn-Ni-H8TPPP4Air37534Co-CAU-29Co-Ni-H8TPPP4Air40034Cd-CAU-29Cd-Ni-H8TPPP4Air40034[Co2(H4-MTPPA)]·3NMP·H2O (1.3NMP·H2O)--4501Zr(H4L)Zr(H4L)10Air42535[Cu3(H3L)(OH)(H2O)3]·H2O·MeOH--2254SZ-1[C4MPYR] [Zr2.5(TPPMH3)F6]·2.5H2O10N230036SZ-2[C4MPYR]2[Zr1.5(TPPM)0.5F4 · 6H2O]10N230036SZ-3[C2PY]2[Zr3.5(TPPAH)F9] · 6.5H2O10N220036Notes:Structural transitions at 275 °C and 350 °C result in VSB-3 and VSB-4. The structure fully decomposes at temperatures in excess of 600 °C.Subsequent to dehydration at 250 °C accompanied by a structural transformation, the structure is reportedly stable up to 600 °C.Thermal decomposition deduced from TGA and variable temperature X-ray diffractometry is stated to indicate stability of MIL-57 up to 750 °C. No TGA trace provided by authors to verify the stated decomposition temperature. Mass losses associated with the loss of pyridine molecules within the structure are observed, with the final being observed at 450 °C. At temperatures greater than 500 °C total collapse of the framework is observed. The temperature at which the ligand dissociates, followed by complete disintegration of the structure at 950 °C.The MOF undergoes a structural change with loss of crystallinity at 220, with amorphilisation occuring at temperatures in excess of 550 °C.Loss of coordinated water and fluorine atoms is observed at 200 °C. 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A, 2016, 4, 1353-1365.34.T. Rhauderwiek, K. Wolkersdoerfer, S. Oeien-Oedegaard, K.-P. Lillerud, M. Wark and N. Stock, Chem. Commun. (Cambridge, U. K.), 2018, 54, 389-392.35.C.-Y. Gao, J. Ai, H.-R. Tian, D. Wu and Z.-M. Sun, Chem. Commun. (Cambridge, U. K.), 2017, 53, 1293-1296.36.T. Zheng, Z. Yang, D. Gui, Z. Liu, X. Wang, X. Dai, S. Liu, L. Zhang, Y. Gao, L. Chen, D. Sheng, Y. Wang, J. Diwu, J. Wang, R. Zhou, Z. Chai, T. E. Albrecht-Schmitt and S. Wang, Nat. Commun., 2017, 8, 15369.Supplementary FiguresSupplementary Figure 1. TG-MS evidence of CO2 (black), benzene (pink) and water (blue) release from the thermal decomposition of tetragonal and cubic variants of MOF-5. Reprinted from reference 1, copyright 2011, with permission from Elsevier.Supplementary Figure 2. TG-MS evidence of benzene release from the thermal decomposition of UiO-66. CO2 release was not reported in this paper. Reprinted with permission from reference 2, copyright 2011 American Chemical Society.Supplementary Figure 3. TG-MS evidence of CO2 release from the thermal decomposition of UiO-67 and UiO-67-NH2. CO2 release appears to take place over a wide-range of temperatures, beginning as low as 325 °C. Multiple release events are observed, centred at c. 450 °C and 550 °C for UiO-67, and c. 400 °C and 550 °C for UiO-67-NH2. Benzene release was not reported in this paper. Reprinted from reference 3, copyright 2018 American Chemical Society.Supplementary Figure 4. The TG-MS evidence of CO2 and benzene release from UiO-66-NH2. Left-hand side shows CO2 release, the right-hand side shows benzene release (as C6H6 or C6H4 fragments). Both are quoted in terms of measurement time, rather than temperature, so exact temperature ranges are unclear. However, CO2 release appears to occurs over a wide temperature range in two distinct events, while benzene release appears to occur in a single event over a relatively narrow band of temperatures. Reprinted from reference 4, copyright 2010 American Chemical Society.Supplementary Figure 5. The pyrazolate ligands H2TMP, H2BDPB and H2BDPP form an isoreticular family of MOFs with Co2+. The increasing linker length results in larger framework pores which appears to be to a lower thermal stability.Supplementary Figure 6. N-donor ligands used in HUM materials, and their associated Td values.12702407920SIFSIX-3-Cu/Zn Td = 150 °C00SIFSIX-3-Cu/Zn Td = 150 °C9671052413635SIFSIX-1-Cu/Zn Td = 150 °C00SIFSIX-1-Cu/Zn Td = 150 °C19907252400935SIFSIX-2-Cu-iTd = 170 °C00SIFSIX-2-Cu-iTd = 170 °C28511502388870SIFSIX-14-Cu-i Td = 170 °C00SIFSIX-14-Cu-i Td = 170 °C38239702389505SIFSIX-17-Cu Td = 210 °C00SIFSIX-17-Cu Td = 210 °C48273482385238SIFSIX-5-Zn-i Td = 300 °C00SIFSIX-5-Zn-i Td = 300 °CReferences:1L. Zhang and Y. H. Hu, Mater. Sci. Eng. B, 2011, 176, 573-578.2L. Valenzano, B. Civalleri, S. Chavan, S. Bordiga, M. H. Nilsen, S. Jakobsen, K. P. Lillerud and C. Lamberti, Chem. Mater., 2011, 23, 1700-1718.3C. Tian, J. Zhao, X. Ou, J. Wan, Y. Cai, Z. Lin, Z. Dang and B. Xing, Environ. Sci. Technol., 2018, 52, 3466-3475.4M. Kandiah, M. H. Nilsen, S. Usseglio, S. Jakobsen, U. Olsbye, M. Tilset, C. Larabi, E. A. Quadrelli, F. Bonino and K. P. Lillerud, Chem. Mater., 2010, 22, 6632-6640. ................
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