**2.1 Correlation between the solvent and the product is often very simple**

The correlation between the solvent and the product is perhaps the easiest to perceive in the system of frameworks synthesised with nickel and 1,3,5-benzenetricarboxylic acid(BTC). In **Table 1**, the structure shifts from the A-topology to the B-topology as we move down to the table and increase the cation size [1]. The shift occurs at smaller cations when we move right to the table to increase the anion size. It appears the size of the solvent, the cation and the anion considered together, is the key factor in determining the topology between A and B. From just this trend alone, it may be inferred that the B topology has a larger pore size, that is more empty space in the framework, than the A topology, which complies with the framework analyses by X-ray diffractions. There are certainly more reasons to this and we will come back to this later in the chapter, but for now, it is enough to just appreciate the simplicity of trend analysis.

The shift in the size of the ionic liquid exerted strong enough a pressure to give rise to two totally different topologies, but sometimes, the shift may be minor. In manganese-BTC system presented in **Table 2**, all three combinations in the [EMI] row gave rise to the exact same structure, α1 [10]. However, in the [PMI] column, only chloride and bromide gave rise to α2, and iodide to a slightly different α3. It is predicted that [EMI] cation is too small to induce a structure transition to occur in the row, but [PMI] is big enough to do so. Even though all the reported cases


*Structures sharing a topological identity were labelled under the same alphabet, while the numbers denote minor difference among them. Each labels denote, [RMI]2[Ni3(BTC)2(OAc)2] (RMI = EMI for A1, PMI for A2, BMI for A3), [RMI]2[Ni3(HBTC)4(H2O)2] (RMI = BMI for B2, PEMI for B3). A1, A2, A3, B1, B2 reported in [1], and B3 in [7].*

#### **Table 1.**

*Organisation of structures in Nickel-BTC system on the length of the alkyl side chain of the cation and the halide anion.*


*Each labels denote, α1-[EMI][Mn(BTC)], α2-[PMI][Mn(BTC)], α2-[PMI][Mn(BTC)]. Combinations that have not been reported were left blank. All entries were reported in [10].*

#### **Table 2.**

*A table for the system of framework synthesised with manganese-BTC system arranged similarly to Table 1.*

**87**

*Ionothermal Synthesis of Metal-Organic Framework DOI: http://dx.doi.org/10.5772/intechopen.79156*

explained using the exact same argument.

*been indicated next to the entries in the table.*

**Table 3.**

in the system belong to the same topology class, but when the smaller differences were accounted, the table again shows a similar stair-shaped pattern that may be

**Cd(OAc)2·H3BTC Cl Br I** [EMI] a1 [12] b1 [12, 13] b1 [12] [PMI] b2 [12] b2 [12] b2 [12] [BMI] — — — *Each labels denote, a1-[EMI][Cd2(BTC)Cl2] for a1, [RMI][Cd(BTC)] (EMI for b1, PMI for b2). Combinations that have not been reported were left blank. Reference in literature to which the entries may be corresponded to has* 

*A table for the system of framework synthesised with cadmium-BTC system arranged similarly to Table 1.*

[14]

[14]

[14]

[14]

[15]

[15]

[15]

[15]

[14]

[14]

[14]

[14]

**cation\***

0% 0 Å3 /2088.3 Å3

0% 0 Å3 /2106.8 Å3

0% 0 Å3 /2082.1 Å3

0% 0 Å3 /2314.1 Å3

1.7% 35.2 Å3 /2103.5 Å3

0.6% 13.0 Å3 /2123.4Å3

0% 0 Å3 /2172.6 Å3

17.0% 1001.9 Å3 /5898.3 Å3

1.4% 31.0 Å3 /2184.2 Å3

0.9% 20.9 Å3 /2201.7Å3

0% 0 Å3 /2267.4Å3

0% 0 Å3 /2275.1 Å3 **Void without cation\***

> 39.6% 827.3 Å3 /2088.3 Å3

> 39.8% 839.6 Å3 /2106.8 Å3

> 40.0% 832.7 Å3 /2082.1 Å3

> 46.8% 1083.9 Å3 /2314.1 Å3

> 38.9% 817.7 Å3 /2103.5 Å3

> 40.0% 848.5 Å3 /2123.4 Å3

> 40.4% 877.1 Å3 /2172.6 Å3

> 52.2% 3081.8 Å3 /5898.3 Å3

> 40.3% 879.5 Å3 /2184.2 Å3

> 41.5% 914.8 Å3 /2201.7 Å3

> 39.7% 901.0 Å3 /2267.4 Å3

> 44.7% 1017.9 Å3 /2275.1 Å3

**M Formula Nuclear # CCDC code Void with** 

Co [EMI]2[Co3(BDC)3Cl2] Tri-nuclear TACHUD

[PMI]2[Co3(BDC)3Cl2] Tri-nuclear TACJAL

[BMI]2[Co3(BDC)3Cl2] Tri-nuclear TACJEP

[AMI]2[Co3(BDC)3Cl2] Tri-nuclear TACJIT

[EMI]2[Co3(BDC)3Br2] Tri-nuclear JOQXOE

[PMI]2[Co3(BDC)3Br2] Tri-nuclear JOQXUK

[BMI]2[Co3(BDC)3Br2] Tri-nuclear JOQPUC

[AMI]2[Co3(BDC)4] Tri-nuclear JOQQAJ

[EMI]2[Co3(BDC)3I2] Tri-nuclear TACJOZ

[PMI]2[Co3(BDC)3I2] Tri-nuclear TACJUF

[BMI]2[Co3(BDC)3I2] Tri-nuclear TACKAM

[AMI]2[Co3(BDC)3I2] Tri-nuclear TACKEQ

in the system belong to the same topology class, but when the smaller differences were accounted, the table again shows a similar stair-shaped pattern that may be explained using the exact same argument.


*Each labels denote, a1-[EMI][Cd2(BTC)Cl2] for a1, [RMI][Cd(BTC)] (EMI for b1, PMI for b2). Combinations that have not been reported were left blank. Reference in literature to which the entries may be corresponded to has been indicated next to the entries in the table.*

## **Table 3.**

*Recent Advancements in the Metallurgical Engineering and Electrodeposition*

materials as the size of the solvent.

appreciate the simplicity of trend analysis.

construct for ternary combinations, which can provide more organised data is obvious. A better understanding of the nature is a foundation for a better utilisation of chemistry for many types of benefits. This section will guide you to the exploration that searches for new meaningful correlations in the sea of ionothermally prepared

The correlation between the solvent and the product is perhaps the easiest to perceive in the system of frameworks synthesised with nickel and 1,3,5-benzenetricarboxylic acid(BTC). In **Table 1**, the structure shifts from the A-topology to the B-topology as we move down to the table and increase the cation size [1]. The shift occurs at smaller cations when we move right to the table to increase the anion size. It appears the size of the solvent, the cation and the anion considered together, is the key factor in determining the topology between A and B. From just this trend alone, it may be inferred that the B topology has a larger pore size, that is more empty space in the framework, than the A topology, which complies with the framework analyses by X-ray diffractions. There are certainly more reasons to this and we will come back to this later in the chapter, but for now, it is enough to just

The shift in the size of the ionic liquid exerted strong enough a pressure to give rise to two totally different topologies, but sometimes, the shift may be minor. In manganese-BTC system presented in **Table 2**, all three combinations in the [EMI] row gave rise to the exact same structure, α1 [10]. However, in the [PMI] column, only chloride and bromide gave rise to α2, and iodide to a slightly different α3. It is predicted that [EMI] cation is too small to induce a structure transition to occur in the row, but [PMI] is big enough to do so. Even though all the reported cases

**Ni(OAc)2·H3BTC Cl Br I** [EMI] A1 A1 A1 [PMI] A2 A2 B1 [BMI] A3 B2 B2 [PEMI] B3 B3 B3 *Structures sharing a topological identity were labelled under the same alphabet, while the numbers denote minor difference among them. Each labels denote, [RMI]2[Ni3(BTC)2(OAc)2] (RMI = EMI for A1, PMI for A2, BMI for A3), [RMI]2[Ni3(HBTC)4(H2O)2] (RMI = BMI for B2, PEMI for B3). A1, A2, A3, B1, B2 reported in [1], and* 

*Organisation of structures in Nickel-BTC system on the length of the alkyl side chain of the cation and the* 

**Mn(OAc)2·H3BTC Cl Br I** [EMI] α1 α2 α1 [PMI] α2 α2 α3 [BMI] — — — [PEMI] — — — *Each labels denote, α1-[EMI][Mn(BTC)], α2-[PMI][Mn(BTC)], α2-[PMI][Mn(BTC)]. Combinations that have* 

*A table for the system of framework synthesised with manganese-BTC system arranged similarly to Table 1.*

*not been reported were left blank. All entries were reported in [10].*

**2.1 Correlation between the solvent and the product is often very simple**

**86**

**Table 2.**

*B3 in [7].*

**Table 1.**

*halide anion.*

*A table for the system of framework synthesised with cadmium-BTC system arranged similarly to Table 1.*



**89**

*Ionothermal Synthesis of Metal-Organic Framework DOI: http://dx.doi.org/10.5772/intechopen.79156*

In [EMI]2[In2(BDC)3Br2] Mono-

Tb [EMI][Tb2(μ2-Cl)

Sm [EMI]2[Sm2(BDC)3(H2- BDC)Cl2]

*literature that each structure was reported.*

**Table 4.**

(BDC)3]

[PMI]2[In2(BDC)3Br2] Mono-

Dy [EMI][Dy3(BDC)5] Poly-nuclear RINTUF

Cd [BMI]2[Cd(BDC)3Br2] Tri-nuclear QETDAV

Cu [EEIM][NaCu(BDC)2] Poly-nuclear VOBRUB

**M Formula Nuclear # CCDC code Void with** 

nuclear

nuclear

*\*Probe radius of 1.2 Å and grid spacing of 0.7 Å was taken for the calculation using the contact surface.*

*Chemical formulas of structures arising from imidazolium-based MOFs with BDC are presented with their nuclear type, CCDC reference code, void volume with and without the residing cation, and the reference in* 

Poly-nuclear YIXFUI

Di-nuclear YIXFIW

SABJOX [21]

SABJIR [21]

[22]

[19]

[19]

[23]

[24]

**cation\***

0% 0 Å3 /2017.0 Å3

0% 0 Å3 /2073.5 Å3

2.8% 134.8 Å3 /4840.8 Å3

19.7% 620.8 Å3 /3152.5 Å3

0% 0 Å3 /2333.3 Å3

0% 0 Å3 /2353.8 Å3

0% 0 Å3 /2200.5 Å3 **Void without cation\***

> 36.0% 725.1 Å3 /2017.0 Å3

> 36.0% 746.0 Å3 /2073.5 Å3

21.2% 1027.3 Å3 /4840.8 Å3

19.7% 620.8 Å3 /3152.5 Å3

30.4% 709.1 Å3 /2333.3 Å3

40.4% 950.6 Å3 /2353.8 Å3

31.3% 688.2 Å3 /2200.5 Å3

**2.2 Ionic liquids function both as a solvent and template**

final topology by residing in the framework [11] (**Table 3**).

literature by applying the ionic liquid to gradual variations.

**2.3 Many reported syntheses are yet to fit into an organised system**

Similar trends may also be found in other metals, despite less well-pronounced than nickel. The similarity may not be noticed at first glance, but it is the same stair-shaped pattern to nickel system. The topology shift just takes place with smaller ionic species. Again, increase in size of the ionic solvent has changed the preferred topology to another class with a larger pore volume to incorporate the ions. As some readers might have noticed by now, here is a good point to introduce another interesting aspect of ionothermal synthesis; ionic liquids function not only as solvents, but also as a template that physically exerts a pressure to determine the

In theory, many choices of organic linkers available in the field of chemistry may add to the large number of ionic combinations to create nearly infinite possible cases, but it takes time for a theory to become reality. While many valuable efforts are being made to contribute, those with 1,3,5-bezenetricarboxylic acid(BTC) and 1,4-benzenedicarboxylic acid(BDC) have done its part particularly extensively and the reported structures were organised in **Tables 4** and **5**. **Tables 4** and **5** are great to appreciate the variety of ionothermally prepared MOFs, plus for searching purposes, but give hardly any information on the chemical reaction that brought about the structures. In order to get a closer grasp on how ionothermal synthesis produced this variety, they must be organised into systems of related syntheses. However, many cases in both tables are rather discrete. Efforts need to be made, starting from what have been reported, to expand the

#### *Recent Advancements in the Metallurgical Engineering and Electrodeposition*

*Ionothermal Synthesis of Metal-Organic Framework DOI: http://dx.doi.org/10.5772/intechopen.79156*


#### **Table 4.**

*Recent Advancements in the Metallurgical Engineering and Electrodeposition*

[PMI]2[Zn3(BDC)3Cl2] Tri-nuclear QUGVAR

Zn(BDC)(H2O) Poly-nuclear IFABIA03

[BMI]2[Zn3(BDC)3Cl2] Tri-nuclear SIVCAD

[EMI]2[Zn3(BDC)3Br2] Tri-nuclear QUGVIZ

[PMI]2[Zn3(BDC)3Br2] Tri-nuclear QUGVOF

[BMI]2[Zn3(BDC)3Br2] Tri-nuclear QUGVUL

[EMI]2[Zn3(BDC)3I2] Tri-nuclear QUGWEW

[PMI]2[Zn3(BDC)3I2] Tri-nuclear QUGWIA

[BMI]2[Zn3(BDC)3I2] Tri-nuclear QUGWOG

[AMI]2[Zn3(BDC)3I2] Tri-nuclear QUGWUM

[PMI][Eu2(BDC)3Cl] Di-nuclear IXITOA02

[BMI][Eu2(BDC)3Cl] Di-nuclear IXITIU02

Eu(BDC)(CO2) Poly-nuclear LARYEK03

Eu(BDC)Cl(H2O) Poly-nuclear IXISIT02

Mononuclear

Eu3(BDC)4Cl(H2O)6 Poly-nuclear

Eu [EMI][Eu2(BDC)3Cl] Di-nuclear IXISOZ02

[EMI] [Eu2(BDC)3(H2BDC) Cl2]

Zn [EMI]2[Zn3(BDC)3Cl2] Tri-nuclear SIVQEV

**M Formula Nuclear # CCDC code Void with** 

**cation\***

0% 0 Å3 /2085.2 Å3

0% 0 Å3 /2097.0Å3

0% 0 Å3 /826.8 Å3

0% 0 Å3 /2167.9 Å3

0.8% 16.5 Å3 /2115.0 Å3

0.6% 11.9 Å3 /2139.4 Å3

0% 0 Å3 /2189.2 Å3

0.6% 12.1 Å3 /2169.2 Å3

0% 0 Å3 /2182.0 Å3

0% 0 Å3 /2253.3 Å3

0% 0 Å3 /2293.1 Å3

0%, 0 Å3 /2339.26 Å3

4.6% 157.3 Å3 /3429.0 Å3

0.2% 14.7 Å3 /6850.9 Å3

0% 0 Å3 /3153.1Å3

0% 0 Å3 /929.6 Å3

0% 0 Å3 /3605.0 Å3

0% 0 Å3 /975.0 Å3

[16]

[17]

[17]

[16]

[17]

[17]

[17]

[17]

[17]

[17]

[17]

[18]

[18]

[18]

[19]

[20]

IXITEQ02 [18]

[18]

Poly-nuclear YIXFOC03

**Void without cation\***

> 39.6% 826.7 Å3 /2085.2 Å3

> 39.7% 833.2 Å3 /2097.0 Å3

0% 0 Å3 /826.8Å3

41.7% 903.4 Å3 /2167.9 Å3

39.9% 844.0 Å3 /2115.0 Å3

40.6% 868.6 Å3 /2139.4 Å3

42.1% 921.1 Å3 /2189.2 Å3

40.0% 868.7 Å3 /2169.2 Å3

40.4% 882.6 Å3 /2182.0 Å3

39.7% 894.2 Å3 /2253.3 Å3

40.7% 933.1 Å3 /2293.1 Å3

30.5% 714.34 Å3 /2339.3 Å3

30.8% 1055.9 Å3 /3429.0 Å3

29.8% 2038.9 Å3 /6850.9 Å3

21.4% 673.7 Å3 /3153.1 Å3

0% 0 Å3 /929.6 Å3

0% 0 Å3 /3605.0 Å3

0% 0 Å3 /975.0 Å3

**88**

*Chemical formulas of structures arising from imidazolium-based MOFs with BDC are presented with their nuclear type, CCDC reference code, void volume with and without the residing cation, and the reference in literature that each structure was reported.*

#### **2.2 Ionic liquids function both as a solvent and template**

Similar trends may also be found in other metals, despite less well-pronounced than nickel. The similarity may not be noticed at first glance, but it is the same stair-shaped pattern to nickel system. The topology shift just takes place with smaller ionic species. Again, increase in size of the ionic solvent has changed the preferred topology to another class with a larger pore volume to incorporate the ions. As some readers might have noticed by now, here is a good point to introduce another interesting aspect of ionothermal synthesis; ionic liquids function not only as solvents, but also as a template that physically exerts a pressure to determine the final topology by residing in the framework [11] (**Table 3**).

#### **2.3 Many reported syntheses are yet to fit into an organised system**

In theory, many choices of organic linkers available in the field of chemistry may add to the large number of ionic combinations to create nearly infinite possible cases, but it takes time for a theory to become reality. While many valuable efforts are being made to contribute, those with 1,3,5-bezenetricarboxylic acid(BTC) and 1,4-benzenedicarboxylic acid(BDC) have done its part particularly extensively and the reported structures were organised in **Tables 4** and **5**. **Tables 4** and **5** are great to appreciate the variety of ionothermally prepared MOFs, plus for searching purposes, but give hardly any information on the chemical reaction that brought about the structures. In order to get a closer grasp on how ionothermal synthesis produced this variety, they must be organised into systems of related syntheses. However, many cases in both tables are rather discrete. Efforts need to be made, starting from what have been reported, to expand the literature by applying the ionic liquid to gradual variations.


**91**

**Table 5.**

**3. The correlation between the reaction solvent and the product**

*Structures arising from imidazolium-based MOFs with BTC presented in a similar manner to Table 1.*

In the previous section, we have explored through the chemical trend observable in nickel, manganese, and cadmium-BTC systems. Some basic explanations have been provided by relating the size of the ionic species to the pore size

*\*Calculation was done with the same setting. Calculation for the entry 'void without cations' has been conducted by* 

*\*\*In the entry with reference code YODZAT, not only ionic cations but also 4,4'-bpy ligands were found in the channel.*

*Ionothermal Synthesis of Metal-Organic Framework DOI: http://dx.doi.org/10.5772/intechopen.79156*

Zn [BMI][Zn2(BTC)(OH)I] Tetra-

[AMI][Zn2(BTC)(OH)Br] Tetra-

[PMI][Zn(BTC)] Mono-

[Zn3(BTC)2(H2O)2]·2H2O Poly-

[Zn4(BTC)2(μ4-O)(H2O)2] Tetra-

Cd [EMI][Cd2(BTC)Cl2] Poly-

*removing only the cations from the channel.*

[BMI]2[Zn4(BTC)3(OH) (H2O)3]

**M Formula Nuclear # CCDC Void with** 

nuclear

nuclear

nuclear

nuclear

nuclear

nuclear

[PMI][Cd(BTC)] Di-nuclear SIZGIS [12] 0%

[BMI][Zn(BTC)] Di-nuclear FUTZEB

[EMI][Cd(BTC)] Di-nuclear NEHMET

[PMI][Mn(BTC)] Di-nuclear WEYQEY

[PMI][Mn(BTC)] Di-nuclear WEYPUN

Mn [EMI][Mn(BTC)] Di-nuclear WEYQAU

[EMI][Zn(BTC)] Di-nuclear MIQKUT

Tri-nuclear MIQLEE

**cation\***

4.7% 106.8 Å3 /2260.6 Å3

4.8% 228.0 Å3 /4739.5 Å3

0% 0 Å3 /2229.3 Å3

0% 0 Å3 /3077.8 Å3

0% 0 Å3 /3353.5 Å3

0% 0 Å3 /1985.1 Å3

37.7% 1293.1 Å3 /3431.7 Å3

0% 0 Å3 /1678.8 Å3

0% 0 Å3 /924.3 Å3

0% 0 Å3 /3181.9 Å3

0 Å3 /3296.9 Å3

0% 0 Å3 /3051.7 Å3

0% 0 Å3 /3229.3 Å3

0% 0 Å3 /3172.0 Å3

VIWZOR [33]

[34]

MIQLII [34]

[34]

MIQLAA [34]

MISRUC [34]

XOHLEM [35]

[36]

SIZGEO [12]

[13]

[10]

[10]

[10]

**Void without cation\***

> 49.4% 1117.8 Å3 /2260.6 Å3

38.4% 1819.6 Å3 /4739.5 Å3

51.0% 1137.0 Å3 /2229.3 Å3

38.2% 1175.6 Å3 /3077.8 Å3

43.9% 1472.9 Å3 /3353.5 Å3

0% 0 Å3 /1985.1 Å3

37.7% 1293.1 Å3 /3431.7 Å3

46.8% 786.5 Å3 /1678.8 Å3

34.0% 314.7 Å3 /924.3 Å3

43.4% 1381.4 Å3 /3181.9 Å3

43.2% 1425.3 Å3 /3296.9 Å3

38.7% 1181.6 Å3 /3051.7 Å3

42.8% 1382.5 Å3 /3229.3 Å3

45.8% 1451.3 Å3 /3172.0 Å3


38.7% 1181.6 Å3 /3051.7 Å3

42.8% 1382.5 Å3 /3229.3 Å3

45.8% 1451.3 Å3 /3172.0 Å3

*\*Calculation was done with the same setting. Calculation for the entry 'void without cations' has been conducted by removing only the cations from the channel.*

*\*\*In the entry with reference code YODZAT, not only ionic cations but also 4,4'-bpy ligands were found in the channel.*

[10]

[10]

[10]

0% 0 Å3 /3051.7 Å3

0% 0 Å3 /3229.3 Å3

0% 0 Å3 /3172.0 Å3

#### **Table 5.**

*Recent Advancements in the Metallurgical Engineering and Electrodeposition*

Ni [EMI]2[Ni3(BTC)2(OAc)2] Tri-

[BMI]2[Ni(HBTC)2(H2O)2] chiral

bpy)3]Br

[EMI][Co(HBTC)(4,4′-bpy)2] (4,4′-bpy)Br

[EMI] [Co2(BTC)4H7(2,2′-bpy)2]

Co [EMI][Co2(HBTC)2(4,4′-

[AMI][Ni3(BTC)2(OAc)(MI)3] Mono-

[EMI][Co(BTC)(H-Im)] Mono-

[EMI]2[Co(BTC)2(H2TED)] Mono-

[EMI]2[In2Co(OH)2(BTC)2Br2] Tri-nuclear

**M Formula Nuclear # CCDC Void with** 

nuclear

[PMI]2[Ni3(BTC)2(OAc)2] Tri-nuclear XUJPIC [1] 0.9%

[BMI]2[Ni3(BTC)3(OAc)2] Tri-nuclear XUJPOI [1] 0%

[BMI]2[Ni3(HBTC)4(H2O)] Tri-nuclear XUJQAV [1] 0%

nuclear Di-nuclear

> Mononuclear

> nuclear

nuclear

[EMI][Co(BTC)] Di-nuclear CIPLIX [29] 0%

Mononuclear

[BMI]2[Co2(BTC)2(H2O)2] Di-nuclear [31] 0%

(In + Co)

[EMI]2[Co3(BTC)2(OAc)2] Tri-nuclear VEMTAJ

[PMI]2[Co2(BTC)2(H2O)2] Di-nuclear XAPSIS

[PMI]2[Ni3(HBTC)4(H2O)] Tri-nuclear VEMSUC01

[BMI]2[Ni(HBTC)2(H2O)2] Tri-nuclear NUNNUH

**cation\***

0% 0 Å3 /3704 Å3

26.4 Å3 /2780.4 Å3

0 Å3 /3802.9 Å3

0% 0 Å3 /3712.3 Å3

0 Å3 /3806.2 Å3

3.4% 132.7 Å3 /3944.7 Å3

3.2% 124.9 Å3 /3953.2 Å3

0% 0 Å3 /4592.0 Å3

0% 0Å3 /5060.8 Å3

0% 0 Å3 /4290.3 Å3

0% 0 Å3 /933.9 Å3

0% 0 Å3 /7246.2 Å3

38.6% 1466.9 Å3 /3797.9 Å3

0 Å3 /3018.2 Å3

16.1% 483.0 Å3 /3002.0 Å3

0% 0 Å3 /1850.4 Å3

0 Å3 /1840.5 Å3

0% 0 Å3 /1884.5 Å3

VEMSUC [25]

[1]

[26]

[26]

EGOYUV [27]

[28]

YODZAT\*\* [28]

YODZEX [28]

YODZIB [28]

[25]

CIPLOD [29]

[30]

VUVZAP [32]

Tri-nuclear NUNPAP

Di-nuclear YODYUM

**Void without cation\***

> 36.5% 1350.8 Å3 /3704 Å3

38.7% 1076.8 Å3 /2780.4 Å3

0% 0 Å3 /3802.9 Å3

36.7% 1363.0 Å3 /3712.3 Å3

0% 0 Å3 /3806.2 Å3

53.6% 2113.7 Å3 /3944.7 Å3

53.6% 2120.3 Å3 /3953.2 Å3

22.4% 1029.7 Å3 /4592.0 Å3

13.6% 688.9 Å3 /5060.8 Å3

17.8% 762.0 Å3 /4290.3 Å3

30. 1% 280.63 Å3 /933.9 Å3

30.7% 2221.6 Å3 /7246.2 Å3

38.6% 1466.9 Å3 /3797.9 Å3

26.0% 784.2 Å3 /3018.2 Å3

16.1% 483.0 Å3 /3002.0 Å3

51.1% 945.9 Å3 /1850.4 Å3

51.8% 952.94 Å3 /1840.5 Å3

36.6% 690.4 Å3 /1884.5 Å3

**90**

*Structures arising from imidazolium-based MOFs with BTC presented in a similar manner to Table 1.*
