**Metal Chalcogenides Tetrahedral Molecular Clusters: Crystal Engineering and Properties**

Chun-Chang Ou and Chung-Sung Yang

Additional information is available at the end of the chapter

http://dx.doi.org/10. 5772/52660

### **1. Introduction**

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402 Advanced Topics on Crystal Growth

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In recent years, the development of crystalline porous materials based on metal chalcoge‐ nides attracts scientific attention for their adjustable porous structures and potential applica‐ tions in technology. In contrast to oxygen, for which only the di- and tri-nuclear homopolyatomic anions, i. e. O2 2-, O2 ‧-and O3 2-, are known in zeolite frameworks, the charac‐ teristic strong tendency of sulfur and the other elements of Group 16 is reflected in the wide range of polychalcogenide ions Xn 2- (X = S, Se, Te). The polychalcogenideXn 2-are easily isolat‐ ed as salts from polar solvents in the presence of suitable counter cations. [1]The choice of sulfides has many obvious advantages in the crystallization chemistry:[2] (a) In comparison with oxide and fluoride ions, the S2-ion has a much largerionic radius, which favors the tet‐ rahedral coordination withcationsand allows the discovery of sulfide homologues of zeo‐ lites. (b) The higher polar ability of the S2-ion shows more flexibility for the structure of tetrahedra angles. For example, the tetrahedraT-S-T angle ranges from109°–161°. But the range of angle for tetrahedra T-O-T is 140°–145°. (T = tetrahedra metal atom, such as In). Ob‐ viously, the frameworks with higher flexibility will have better ability to accommodate vari‐ ous shapes of the templates, and the arrangement of tetrahedralunits in the dense matter can remain their original architectures.

Nowadays, chemists use inorganic clusters as molecular building blocks to create open framework with cavities and channels, including porous semiconductor, fast ion exchanger, shape- and size-selective catalysis, and optoelectronic applications. Among these clusters, only the metal chalcogenides tetrahedral molecular clusters can serve as artificial tetrahedral atoms, and assemble the tetrahedral clusters into porous open-framework through inorganic chalcogenides ligands.

© 2013 Ou and Yang; licensee InTech. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2013 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

The study of metal chalcogenides tetrahedral molecular clusters provides a valuable opportuni‐ ty to explore the synthetic and structural chemistry at the interface of chalcogenide molecular chemistry and solid-state chemistry. [3,4]A general introduction and overview of metal chalco‐ genides tetrahedral molecular clusters is intended in this chapter. In the following sections, a de‐ scription of four basic types of metal chalcogenides tetrahedral molecular clusters will be provided. Design, synthesis strategy, and crystal engineering of building open-framework chal‐ cogenides materials will be discussed. In addition, the interrelated properties of metal chalcoge‐ nides tetrahedral molecular clusters will be emphasized as the highlight of this paper.

### **2. Classification of structure and mathematical extrapolation**

### **2.1. Supertetrahedral clusters**

The simplest tetrahedral clusters of metal chalcogenides tetrahedral molecular clusters is su‐ pertetrahedral clusters, i. e. Tn clusters, with tetrahedral shaped fragments similar to the cubic ZnS-type lattice. [3-5] The supertetrahedral clusters were first denoted as 2{n}by Dance et al. [6] Recently, these compounds are denoted as T*n* by Yaghi'sgroup. [4] In the formula, n is the number of metal layers. The mathematical of supertetrahedral clusters can be regarded as the analog of the ideal artificial tetrahedral atoms. The number of tetrahedra (T atoms) in a T*n*su‐ pertetrahedron is the nth tetrahedral number:*tn* = *n*(*n* + *1*)(*n* + 2)/6. The number of distinct ver‐ texes (X atoms) in one supertetrahedron is *tn+1*. The formulas for discrete T*n* clusters are given as follows: T1 (MX4), T2 (M4X10), T3 (M10X20), T4 (M20X35) and T5 (M35X56),where M is a metal cation and X is a chalcogen anion. [5]The illustration figures for Tn clusters are shown in Figure 1.

**Figure 1.** Illustration forT*n* series clusters, from T2 to T5. [3]

T2 (MX4) [Ga4S10]

T3 (M4X10) [In10S20]

T4 (M10X20) [M4In16S33]

[In4Q10]

[Ge4Q10]

[Sn4Q10]

[Ga10S16(NC7H9)

[Cd4In16S35]

(In34S54)

(In28Cd6S56)

**Table 1.** Supertetrahedral clusters base on metal chalcogenides tetrahedral molecular clusters

4]

T5 (M35X56) Cu5In30S54, [14]

**Stoichiometry of Tn examples Ref.**

8- [7]

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405

8-(Q=S, Se) [8]

4- (Q=S, Se) 9

4- (Q=S, Te) [10]

10- [11]

10- (M=Mn2+,Co2+,Zn2+,Cd2+), [13]

14- [5]

6- [15]

12- [16]

In10S18(HPP)6(H2O)15 [4]

2- [12]

In an open-continuous framework, each of the four outermost vertexes of a supertetrahe‐ dron is shared with another supertetrahedron. Therefore, the overall composition is TxXy with *x = tn*and *y = tn+1-2*. In Tn clusters, all the T atoms are 4-coordinated. Nevertheless, the X atoms possess 2-coordination sites (on the supertetrahedron edges and the outermost ver‐ texes), 3-coordination sites (in the supertetrahedron faces), and 4-coordination sites (inside the cluster). In each corner linkedTn cluster (TxXy), the number of 2-coordinated X atoms is *6n-4*, and the number of 3-coordinated X atoms is *2(n - 1)(n - 2).* The 4-coordinated sites will not appear, until the n value reaches *4*or higher. When n = 4 or higher, the number of 4-coor‐ dinated X atoms is *tn-3*. For example, a T2 cluster consists of only 2-coordinated anions (e. g., S2-), and a T3 cluster has both 2- and 3-coordinated anions. Starting from the T4 cluster, tet‐ rahedral coordination begins to adopt anions inside the cluster to create 4-coordinated anions, beside the existed 2- and 3-coordinated anions. [5]

In Table 1, the known T2 clusters, [Ga4S10] 8-,[7] [In4Q10] 8-,[8] [Ge4Q10] 4- (Q=S, Se),[9] [Sn4Q10] 4- (Q=S, Te),[10]and examples of T3 clusters, [In10S20] 10-,[11] [Ga10S16(NC7H9) 4 ] 2-,[12] and In10S18(HPP)6(H2O)15. [4](HPP=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) are pro‐ vided. On the other hand, the reported T4 clusters, [M4In16S33] 10- (M=Mn2+,Co2+,Zn2+,Cd2+)[13] and [Cd4In16S35] 14-[5]are provided in Table 1, simultaneously. Up to date, the largest Tn clus‐ ters that has been prepared is T5 cluster. The examples are Cu5In30S54,[14] (In34S54) 6- [15] and (In28Cd6S56) 12-. [16]

**Figure 1.** Illustration forT*n* series clusters, from T2 to T5. [3]

The study of metal chalcogenides tetrahedral molecular clusters provides a valuable opportuni‐ ty to explore the synthetic and structural chemistry at the interface of chalcogenide molecular chemistry and solid-state chemistry. [3,4]A general introduction and overview of metal chalco‐ genides tetrahedral molecular clusters is intended in this chapter. In the following sections, a de‐ scription of four basic types of metal chalcogenides tetrahedral molecular clusters will be provided. Design, synthesis strategy, and crystal engineering of building open-framework chal‐ cogenides materials will be discussed. In addition, the interrelated properties of metal chalcoge‐

The simplest tetrahedral clusters of metal chalcogenides tetrahedral molecular clusters is su‐ pertetrahedral clusters, i. e. Tn clusters, with tetrahedral shaped fragments similar to the cubic ZnS-type lattice. [3-5] The supertetrahedral clusters were first denoted as 2{n}by Dance et al. [6] Recently, these compounds are denoted as T*n* by Yaghi'sgroup. [4] In the formula, n is the number of metal layers. The mathematical of supertetrahedral clusters can be regarded as the analog of the ideal artificial tetrahedral atoms. The number of tetrahedra (T atoms) in a T*n*su‐ pertetrahedron is the nth tetrahedral number:*tn* = *n*(*n* + *1*)(*n* + 2)/6. The number of distinct ver‐ texes (X atoms) in one supertetrahedron is *tn+1*. The formulas for discrete T*n* clusters are given as follows: T1 (MX4), T2 (M4X10), T3 (M10X20), T4 (M20X35) and T5 (M35X56),where M is a metal cation and X is a chalcogen anion. [5]The illustration figures for Tn clusters are shown in Figure 1.

In an open-continuous framework, each of the four outermost vertexes of a supertetrahe‐ dron is shared with another supertetrahedron. Therefore, the overall composition is TxXy with *x = tn*and *y = tn+1-2*. In Tn clusters, all the T atoms are 4-coordinated. Nevertheless, the X atoms possess 2-coordination sites (on the supertetrahedron edges and the outermost ver‐ texes), 3-coordination sites (in the supertetrahedron faces), and 4-coordination sites (inside the cluster). In each corner linkedTn cluster (TxXy), the number of 2-coordinated X atoms is *6n-4*, and the number of 3-coordinated X atoms is *2(n - 1)(n - 2).* The 4-coordinated sites will not appear, until the n value reaches *4*or higher. When n = 4 or higher, the number of 4-coor‐ dinated X atoms is *tn-3*. For example, a T2 cluster consists of only 2-coordinated anions (e. g., S2-), and a T3 cluster has both 2- and 3-coordinated anions. Starting from the T4 cluster, tet‐ rahedral coordination begins to adopt anions inside the cluster to create 4-coordinated

8-,[7] [In4Q10]

14-[5]are provided in Table 1, simultaneously. Up to date, the largest Tn clus‐

In10S18(HPP)6(H2O)15. [4](HPP=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) are pro‐

ters that has been prepared is T5 cluster. The examples are Cu5In30S54,[14] (In34S54)

8-,[8] [Ge4Q10]

10-,[11] [Ga10S16(NC7H9)

4- (Q=S, Se),[9] [Sn4Q10]

4 ]

10- (M=Mn2+,Co2+,Zn2+,Cd2+)[13]

4-

2-,[12] and

6- [15] and

anions, beside the existed 2- and 3-coordinated anions. [5]

(Q=S, Te),[10]and examples of T3 clusters, [In10S20]

vided. On the other hand, the reported T4 clusters, [M4In16S33]

In Table 1, the known T2 clusters, [Ga4S10]

and [Cd4In16S35]

12-. [16]

(In28Cd6S56)

nides tetrahedral molecular clusters will be emphasized as the highlight of this paper.

**2. Classification of structure and mathematical extrapolation**

**2.1. Supertetrahedral clusters**

404 Advanced Topics on Crystal Growth


**Table 1.** Supertetrahedral clusters base on metal chalcogenides tetrahedral molecular clusters

#### **2.2. Pentasupertetrahedral clusters (Pn)**

The second series of tetrahedral clusters is known as pentasupertetrahedral clusters, shown in Figure 2. This series cluster was denoted as 5 {n} by Dance et al. [6] and was named as P*n* by Feng'sgroup. [17] The P*n* cluster is composed of four same order T*n* clusters at the corner and one anti-T*n* cluster at the core. In comparison, a pentasupertetrahedral cluster is consid‐ erably larger than a supertetrahedral cluster of the same order. For example: the P1 cluster consists four T1 clusters (MX4) and one anti-T1 (XM4) cluster at the center, resulting in the composition ((MX4)4(XM4) (i. e., M8X17). The supertetrahedral clusters as large as T5 are known, but the largest known cluster of the P*n* series is the P2 cluster. [17]

**2.3. Capped supertetrahedral clusters (Cn)**

**Figure 3.** Illustration for C*n* series clusters, from C1 to C2. (adopted from Ref 30)[30]

Cd32Se14(SePh)36(PPh3)4[28] have been successfully synthesized, so far.

C1 (M17X32) [S4Cd17(SPh)28]

ters is [S4Cd17(SPh)28]

As shown in Table 3, the first metal chalcogenides tetrahedral molecular clusters of C1 clus‐

days, two new C1 clusters were reported. They are Cd17S4(SCH2CH2OH)26[24]and [S4Cd17(SPh)24(CH3OCS2)4/2]n nCH3OH. [25]As for the C2 clusters, three clusters, Cd32S14(SCH2CH(OH)CH3)36. 4H2O,[26] Cd32S14(SC6H5)36. (DMF)4,[27] and

**Stoichiometry of Cn examples Ref.**

C2 (M32X54) Cd32S14(SCH2CH(OH)CH3)36. 4H2O [26]

**Table 3.** Capped-supertetrahedral clusters base on metal chalcogenides tetrahedral molecular clusters

2- [18], (SPh=benzenethiol ligand), by Dance group in 1988. In later

Cd17S4(SCH2CH2OH)26 [24] [S4Cd17(SPh)24(CH3OCS2)4/2]nnCH3OH [25]

Cd32Se14(SePh)36(PPh3)4 [27] Cd32S14(SC6H5)36. (DMF)4 [28]

2- [18]

The third series of tetrahedral clusters is capped-supertetrahedral clusters, as shown in Fig‐ ure 3. This series clusterwas denoted as 7{n}by Dance et al. [6] Recently, the series clusterwas named as C*n* by Feng's group. [3] The capped supertetrahedral clusters are defined as a reg‐ ular supertetrahedral cluster (T*n*) at the core covered with a shell of atoms, which is also re‐ lated to the Tn cluster. Accurately, each face of the T*n* core unit is covered with a single sheet of atoms called the T(*n* + 1) sheet and each corner of this cluster is covered with a MX group. The T(*n* + 1) sheet is defined as the bottom atomic sheet of a T(*n* + 1) cluster. [3]

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407

**Figure 2.** Illustration for P*n* series clusters, from P1 to P2. A polyhedral representation is used for the central antisuper‐ tetrahedral cluster. [30]

Some examples of P1 clusters, [SCd8(SBu)12](CN)4/2,[18](SBu= n-butanethiolate ) [M4Sn4S17] 10- (M=Mn2+, Fe2+, Co2+, Zn2+),[19] and [M4Sn4Se17]10- (M=Mn2+, Co2+, Zn2+),[20,21]and P2 clusters, [Li4In22S44] 18- in ICF-26[22](ICF= Inorganic ChalcogenideFramework) and [Cu11In15Se16(SePh)24(PPh3)4]. [23] (Ph= phenyl group, PPh3=triphenylphosphine group) are given in Table 2.


**Table 2.** Pentasupertetrahedral clusters base on metal chalcogenides tetrahedral molecular clusters

### **2.3. Capped supertetrahedral clusters (Cn)**

**2.2. Pentasupertetrahedral clusters (Pn)**

406 Advanced Topics on Crystal Growth

tetrahedral cluster. [30]

[Li4In22S44]

given in Table 2.

The second series of tetrahedral clusters is known as pentasupertetrahedral clusters, shown in Figure 2. This series cluster was denoted as 5 {n} by Dance et al. [6] and was named as P*n* by Feng'sgroup. [17] The P*n* cluster is composed of four same order T*n* clusters at the corner and one anti-T*n* cluster at the core. In comparison, a pentasupertetrahedral cluster is consid‐ erably larger than a supertetrahedral cluster of the same order. For example: the P1 cluster consists four T1 clusters (MX4) and one anti-T1 (XM4) cluster at the center, resulting in the composition ((MX4)4(XM4) (i. e., M8X17). The supertetrahedral clusters as large as T5 are

**Figure 2.** Illustration for P*n* series clusters, from P1 to P2. A polyhedral representation is used for the central antisuper‐

Some examples of P1 clusters, [SCd8(SBu)12](CN)4/2,[18](SBu= n-butanethiolate ) [M4Sn4S17]

(M=Mn2+, Fe2+, Co2+, Zn2+),[19] and [M4Sn4Se17]10- (M=Mn2+, Co2+, Zn2+),[20,21]and P2 clusters,

[Cu11In15Se16(SePh)24(PPh3)4]. [23] (Ph= phenyl group, PPh3=triphenylphosphine group) are

**Stoichiometry of Pn examples Ref.** P1 (M8X17) [SCd8(SBu)12](CN)4/2 [18]

[M4Sn4S17]

[M4Sn4Se17]

**Table 2.** Pentasupertetrahedral clusters base on metal chalcogenides tetrahedral molecular clusters

P2 (M26X44) [Li4In22S44]

18- in ICF-26[22](ICF= Inorganic ChalcogenideFramework) and

10- (M=Mn2+, Fe2+, Co2+, Zn2+) [19]

18- [22]

[Cu11In15Se16(SePh)24(PPh3)4]. [23]

10- (M=Mn2+, Co2+, Zn2+) [20, 21]

10-

known, but the largest known cluster of the P*n* series is the P2 cluster. [17]

The third series of tetrahedral clusters is capped-supertetrahedral clusters, as shown in Fig‐ ure 3. This series clusterwas denoted as 7{n}by Dance et al. [6] Recently, the series clusterwas named as C*n* by Feng's group. [3] The capped supertetrahedral clusters are defined as a reg‐ ular supertetrahedral cluster (T*n*) at the core covered with a shell of atoms, which is also re‐ lated to the Tn cluster. Accurately, each face of the T*n* core unit is covered with a single sheet of atoms called the T(*n* + 1) sheet and each corner of this cluster is covered with a MX group. The T(*n* + 1) sheet is defined as the bottom atomic sheet of a T(*n* + 1) cluster. [3]

**Figure 3.** Illustration for C*n* series clusters, from C1 to C2. (adopted from Ref 30)[30]

As shown in Table 3, the first metal chalcogenides tetrahedral molecular clusters of C1 clus‐ ters is [S4Cd17(SPh)28] 2- [18], (SPh=benzenethiol ligand), by Dance group in 1988. In later days, two new C1 clusters were reported. They are Cd17S4(SCH2CH2OH)26[24]and [S4Cd17(SPh)24(CH3OCS2)4/2]n nCH3OH. [25]As for the C2 clusters, three clusters, Cd32S14(SCH2CH(OH)CH3)36. 4H2O,[26] Cd32S14(SC6H5)36. (DMF)4,[27] and Cd32Se14(SePh)36(PPh3)4[28] have been successfully synthesized, so far.


**Table 3.** Capped-supertetrahedral clusters base on metal chalcogenides tetrahedral molecular clusters

#### **2.4. Super-supertetrahedral clusters (Tp,q)**

Besides theseries of tetrahedral molecular clusters, a special multi-series metal chalcoge‐ nides hollow cluster has been reported, simultaneously. These metal chalcogenides hollow clusters are known as super-supertetrahedral clusters, denoted as T*p,q*. [29]This series of cluster is built in a T*q* supertetrahedron of T*p* supertetrahedra. The number of tetrahedra (T atoms) in a T*p* supertetrahedron is the *p*th tetrahedral number, *tp=p(p+1)(p+2)/6*, and the number of X atoms is t*p+1*. In a T*p, q* super-supertetrahedron the number of T atoms is *tqtp,*and the number of X atoms is t*q(tp+1-2)+2*. The first metal chalcogenides tetrahedral mo‐ lecular clusters of T*p,q* clusters is CdInS-420, i. e. T4,2 ( given in Figure 4), prepared by Yaghi group. [29]

chalcogenides tetrahedral molecular clusters include the crystallization from solution[6,

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409

2-, M=Fe, Co, Zn **(1)** and probably Cd react with sulphur and different metal cation (i. e., Fe, Zn, Cd)

4-, M=Zn, Cd **(3)**. [31]

2- (M=Zn2+, Cd2+) with sulphur, including the met‐

2-**(2)** and [S4M10(SPh)16]

Prior to the development of open framework chalcogenides, tetrahedral clusters were not commonly encountered among open framework solids. In 1982, Dance group reported the

als zinc and cadmium in acetonitrile, to yield a different and unprecedented product (Me4N)4[S4M10(SPh)16] (M = Zn2+, Cd2+), shown in Figure 5. [31]A similar crystallization from

30-31] and the hydrothermal synthetic route. [2-5, 13]

**Figure 5.** [M4(SPh)10]

in acetonitrile to yield the [Fe4S4(SPh)4]

extension reaction of T2 cluster, [M4(SPh)10]

**Figure 4.** a) The CdInS-420 cluster as a ball and stick model. In (blue); Cd (orange); S (green). The large yellow sphere indicates the central cavity. (b) The same view as (a) shown as metal-centered tetrahedra. [29]

### **3. Design and synthesis: Crystal engineering**

The explosive growth in the number of microporous and open framework materials is main‐ ly contributed by the numerous variable synthetic and structural parameters. It is known that each Tn cluster behaves as an artificial tetrahedral atom (T atom). These T atoms link with others by four vertex chalcogenides (ex: sulfur) atoms into the nanoclusters to produce extended open frameworks. Among these clusters, the use of structure-directing agents with different charge, size, and shape is particularly effective to assist the formation of oxide frameworks. [3-5]Furthermore, the conventional synthetic methods to prepare the metal chalcogenides tetrahedral molecular clusters include the crystallization from solution[6, 30-31] and the hydrothermal synthetic route. [2-5, 13]

**2.4. Super-supertetrahedral clusters (Tp,q)**

408 Advanced Topics on Crystal Growth

group. [29]

Besides theseries of tetrahedral molecular clusters, a special multi-series metal chalcoge‐ nides hollow cluster has been reported, simultaneously. These metal chalcogenides hollow clusters are known as super-supertetrahedral clusters, denoted as T*p,q*. [29]This series of cluster is built in a T*q* supertetrahedron of T*p* supertetrahedra. The number of tetrahedra (T atoms) in a T*p* supertetrahedron is the *p*th tetrahedral number, *tp=p(p+1)(p+2)/6*, and the number of X atoms is t*p+1*. In a T*p, q* super-supertetrahedron the number of T atoms is *tqtp,*and the number of X atoms is t*q(tp+1-2)+2*. The first metal chalcogenides tetrahedral mo‐ lecular clusters of T*p,q* clusters is CdInS-420, i. e. T4,2 ( given in Figure 4), prepared by Yaghi

**Figure 4.** a) The CdInS-420 cluster as a ball and stick model. In (blue); Cd (orange); S (green). The large yellow sphere

The explosive growth in the number of microporous and open framework materials is main‐ ly contributed by the numerous variable synthetic and structural parameters. It is known that each Tn cluster behaves as an artificial tetrahedral atom (T atom). These T atoms link with others by four vertex chalcogenides (ex: sulfur) atoms into the nanoclusters to produce extended open frameworks. Among these clusters, the use of structure-directing agents with different charge, size, and shape is particularly effective to assist the formation of oxide frameworks. [3-5]Furthermore, the conventional synthetic methods to prepare the metal

indicates the central cavity. (b) The same view as (a) shown as metal-centered tetrahedra. [29]

**3. Design and synthesis: Crystal engineering**

**Figure 5.** [M4(SPh)10] 2-, M=Fe, Co, Zn **(1)** and probably Cd react with sulphur and different metal cation (i. e., Fe, Zn, Cd) in acetonitrile to yield the [Fe4S4(SPh)4] 2-**(2)** and [S4M10(SPh)16] 4-, M=Zn, Cd **(3)**. [31]

Prior to the development of open framework chalcogenides, tetrahedral clusters were not commonly encountered among open framework solids. In 1982, Dance group reported the extension reaction of T2 cluster, [M4(SPh)10] 2- (M=Zn2+, Cd2+) with sulphur, including the met‐ als zinc and cadmium in acetonitrile, to yield a different and unprecedented product (Me4N)4[S4M10(SPh)16] (M = Zn2+, Cd2+), shown in Figure 5. [31]A similar crystallization from solution reactions with elemental selenium yields analogous complexes (Me4N4) [Se4M10(SPh)16] (M = Zn2+, Cd2+). Therefore, a set of four homologous complexes, (Me4N4) [X4M10(SPh)16] (M = Zn2+, Cd2+; X = S2-, Se2-) have been prepared by this method. The four anions have the same molecular aggregation structure, i. e. a supertetrahedral 10-metal sec‐ tion of the cubic (sphalerite) metal chalcogenide structure. Nowadays, the unprecedented product (Me4N)4[S4M10(SPh)16] (M = Zn2+, Cd2+) is known as the T3 series clusters. The hydro‐ thermal synthesis of open framework chalcogenidesis started with simple elemental forms (e. g., sulfur) and inorganic salts. The initial process usually involves redox chemistry in the formation of clusters. Clusters of various types and sizes could coexist in a solution. Equili‐ bria between various clusters in solution would shift to the direction that favors the creation of one or more clusters, when crystallization involving these clusters occurs. [3]

In In-S system of metal chalcogenides tetrahedral molecular clusters, Yaghi'sgroup used the In-S composition to build a unique porous sulfide-based frame work materials. [4-5] Its uniqueness comes from 50% or more framework cation sites in zeolite-like oxides with a va‐ lence ≧4. The linkage in In-O-In or Al-O-Al is not similar to that in zeolite-like oxides be‐ cause of the Loewenstein rule. The Loewenstein rule states that the ratio of M4+/M3+ should be larger or equal to one. [17] The most common in the In-S system is the occurrence of the

ble to form the required 3-coordinated sulfur site for the formation of T3 clusters. Moreover, the In3+ composition is extended to Ga-S, Ga-Se, and In-Se compositions by Feng'sgroup. [11,17,33]The use of the nonaqueous synthesis method is responsible for the success in the syntheses of Ga-S composition. On the other hand, the synthesis of the [Cd4In16S35]14in T4 cluster shows that the access of regular clusters larger than T3 is possible by the help of di‐ valent cations, in addition to the In-S composition. [5]Moreover, the combination of mono‐

In terms of chemical compositions, metal chalcogenides tetrahedral molecular clusters with tetravalent (M4+) and trivalent (M3+) metal cations closely resembles the structure of alumi‐ nosilicate zeolites. The M4+/M3+ was not expected to be simple because eitherM4+ or M3+ could independently form amine-directed crystals with sulfur and thus the probability of phase separation was high. [7, 17]Nevertheless, the use of the nonaqueous synthesis method could lead to the integration of M4+ and M3+ ions into the same framework. [11, 17, 33]A series of open framework sulfides and selenides were made by the combination of tetravalent (i. e., Ge4+, Sn4+) and trivalent metal (i. e., Ga3+, In3+) ions. [34] The M4+/M3+ ratio in these chalcoge‐ nides can be much smaller than that in zeolites. So far, the M4+/M3+ ratio falls within the range from 1. 3 to 0. 21. Besides the low M4+/M3+ ratio in this series, some sulfides possess

As mentioned in the above paragraph, the type of metal cations existed in the metal chalco‐ genides tetrahedral molecular clusters growth system shows a limitation on the formation of individual clusters. It is worth nothing to mention that cluster larger than T3 can be formed, if only trivalent cation isused in solvothermal system. However, if the synthesis is employ‐ edwith trivalent and divalent cations, the system has the flexibility to create a variety of

In oxides compounds, the oxygen sites of the anionic framework can form strong hydrogen bonding with N-H groups of protonated amine molecules. [3] Such O…H-N bonding is an important factor in the directed assembly of oxide frameworks. The hydrogen bonding be‐ tween chalcogenides frameworks and guest molecules (e. g., S…H-N) is very weak. [3]Based on the host–guest charge-density matching principle, proposed by Stucky et al., the content and distribution of heteroatoms in the framework can be adjusted by the guest species. [35] Thus, the co-assembly of metal chalcogenides tetrahedral molecular clusters with structuredirecting agent (guest), such as amine molecules, depends to a large extent on the host-guest

adequate stability toward ion exchange and thermal treatment. [17,34]

10-. The lower charge on In3+, compared with Ge4+ and Sn4+, makes it possi‐

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411

) and trivalent cations (eg., In3+) could provide the required local charge

T3 cluster, [In10S20]

valent (eg., Cu+

matching around the tetrahedral S2- site. [14, 17]

clusters, such as T3, T4, and T5. [17]

**3.2. Structure-directing agent: Organic amines**

### **3.1. Chalcogenides with different valence state of metal cations**

Metal chalcogenides tetrahedral molecular clusters in the self-assembly process is critical for the synthesis of microporous and mesoporous oxides. [32]The known example is alumino‐ phosphates open-frameworks with divalent metal cations (M2+). The existence of M2+ can provide a rather flexible adjustment of the framework charge density and therefore makes it easier to achieve the charge matching of whole compound. In metal chalcogenides tetrahe‐ dral molecular clusters, the ratio between metal cations of different valences subjects to the limitation of the local charge balance within each cluster and may not be as flexible as that in the oxides analogue. [3, 29]

The classes of open framework materials are dominated by typical zeolites, such as ZSM-5, (named after Zeolite Socony Mobil by mobiloil company). The sodalite structure can be made in the neutral SiO2 form. Neutral porous frameworks are also found in AlPO4 and GeO2 forms. Therefore, it is reasonable to expect the existence of open framework sulfides with framework composition of GeS2 or SnS2. The early development of metal chalcogenides tetrahedral molecular clusters is the preparation of open framework sulfides by using the mono- or divalent cations (e. g., Cu+ , Mn2+) to join the metal chalcogenides tetrahedral mo‐ lecular clusters together (i. e. Ge4S104-). [17] These low-valentcations can generate negative charges on the framework. Subsequently,the charge is balanced by structure-directing amine molecules. For example, the compounds prepared with the formula of [(CH3)4N]2[MGe4S10] (M= Mn2+, Fe2+, Cd2+), by Yaghigroup. [7]In this case, the MnGe4S10‧ 2(CH3)4N, has a non-interpenetrating diamond type lattice (the single diamond type) with alternating T2 and T1 clusters to occupy the tetrahedral nodes. In the Ge-S or Ge-Se system of metal chalcogenides tetrahedral molecular clusters, the largest metal chalcogenidessuper‐ tetrahedral molecular cluster is T2. As a result, a perspective charge-balance problem of met‐ al chalcogenides tetrahedral molecular clusters system is proposed. [17]In the Ge-S or Ge-Se system of metal chalcogenides tetrahedral molecular clusters, Feng's group found that clus‐ ters larger than T2 cannot be prepared in this system. The reason is that the charge at cation sites is too high to satisfy the coordination environment of 3-coordinated anion sites in clus‐ ters larger than T2. For the same reason, it is not surprise to find that no regular T3 cluster can besuccessfully prepared in the pure Sn-S (or Sn-Se) system.

In In-S system of metal chalcogenides tetrahedral molecular clusters, Yaghi'sgroup used the In-S composition to build a unique porous sulfide-based frame work materials. [4-5] Its uniqueness comes from 50% or more framework cation sites in zeolite-like oxides with a va‐ lence ≧4. The linkage in In-O-In or Al-O-Al is not similar to that in zeolite-like oxides be‐ cause of the Loewenstein rule. The Loewenstein rule states that the ratio of M4+/M3+ should be larger or equal to one. [17] The most common in the In-S system is the occurrence of the T3 cluster, [In10S20] 10-. The lower charge on In3+, compared with Ge4+ and Sn4+, makes it possi‐ ble to form the required 3-coordinated sulfur site for the formation of T3 clusters. Moreover, the In3+ composition is extended to Ga-S, Ga-Se, and In-Se compositions by Feng'sgroup. [11,17,33]The use of the nonaqueous synthesis method is responsible for the success in the syntheses of Ga-S composition. On the other hand, the synthesis of the [Cd4In16S35]14in T4 cluster shows that the access of regular clusters larger than T3 is possible by the help of di‐ valent cations, in addition to the In-S composition. [5]Moreover, the combination of mono‐ valent (eg., Cu+ ) and trivalent cations (eg., In3+) could provide the required local charge matching around the tetrahedral S2- site. [14, 17]

In terms of chemical compositions, metal chalcogenides tetrahedral molecular clusters with tetravalent (M4+) and trivalent (M3+) metal cations closely resembles the structure of alumi‐ nosilicate zeolites. The M4+/M3+ was not expected to be simple because eitherM4+ or M3+ could independently form amine-directed crystals with sulfur and thus the probability of phase separation was high. [7, 17]Nevertheless, the use of the nonaqueous synthesis method could lead to the integration of M4+ and M3+ ions into the same framework. [11, 17, 33]A series of open framework sulfides and selenides were made by the combination of tetravalent (i. e., Ge4+, Sn4+) and trivalent metal (i. e., Ga3+, In3+) ions. [34] The M4+/M3+ ratio in these chalcoge‐ nides can be much smaller than that in zeolites. So far, the M4+/M3+ ratio falls within the range from 1. 3 to 0. 21. Besides the low M4+/M3+ ratio in this series, some sulfides possess adequate stability toward ion exchange and thermal treatment. [17,34]

As mentioned in the above paragraph, the type of metal cations existed in the metal chalco‐ genides tetrahedral molecular clusters growth system shows a limitation on the formation of individual clusters. It is worth nothing to mention that cluster larger than T3 can be formed, if only trivalent cation isused in solvothermal system. However, if the synthesis is employ‐ edwith trivalent and divalent cations, the system has the flexibility to create a variety of clusters, such as T3, T4, and T5. [17]

#### **3.2. Structure-directing agent: Organic amines**

solution reactions with elemental selenium yields analogous complexes (Me4N4) [Se4M10(SPh)16] (M = Zn2+, Cd2+). Therefore, a set of four homologous complexes, (Me4N4) [X4M10(SPh)16] (M = Zn2+, Cd2+; X = S2-, Se2-) have been prepared by this method. The four anions have the same molecular aggregation structure, i. e. a supertetrahedral 10-metal sec‐ tion of the cubic (sphalerite) metal chalcogenide structure. Nowadays, the unprecedented product (Me4N)4[S4M10(SPh)16] (M = Zn2+, Cd2+) is known as the T3 series clusters. The hydro‐ thermal synthesis of open framework chalcogenidesis started with simple elemental forms (e. g., sulfur) and inorganic salts. The initial process usually involves redox chemistry in the formation of clusters. Clusters of various types and sizes could coexist in a solution. Equili‐ bria between various clusters in solution would shift to the direction that favors the creation

Metal chalcogenides tetrahedral molecular clusters in the self-assembly process is critical for the synthesis of microporous and mesoporous oxides. [32]The known example is alumino‐ phosphates open-frameworks with divalent metal cations (M2+). The existence of M2+ can provide a rather flexible adjustment of the framework charge density and therefore makes it easier to achieve the charge matching of whole compound. In metal chalcogenides tetrahe‐ dral molecular clusters, the ratio between metal cations of different valences subjects to the limitation of the local charge balance within each cluster and may not be as flexible as that in

The classes of open framework materials are dominated by typical zeolites, such as ZSM-5, (named after Zeolite Socony Mobil by mobiloil company). The sodalite structure can be made in the neutral SiO2 form. Neutral porous frameworks are also found in AlPO4 and GeO2 forms. Therefore, it is reasonable to expect the existence of open framework sulfides with framework composition of GeS2 or SnS2. The early development of metal chalcogenides tetrahedral molecular clusters is the preparation of open framework sulfides by using the

lecular clusters together (i. e. Ge4S104-). [17] These low-valentcations can generate negative charges on the framework. Subsequently,the charge is balanced by structure-directing amine molecules. For example, the compounds prepared with the formula of [(CH3)4N]2[MGe4S10] (M= Mn2+, Fe2+, Cd2+), by Yaghigroup. [7]In this case, the MnGe4S10‧ 2(CH3)4N, has a non-interpenetrating diamond type lattice (the single diamond type) with alternating T2 and T1 clusters to occupy the tetrahedral nodes. In the Ge-S or Ge-Se system of metal chalcogenides tetrahedral molecular clusters, the largest metal chalcogenidessuper‐ tetrahedral molecular cluster is T2. As a result, a perspective charge-balance problem of met‐ al chalcogenides tetrahedral molecular clusters system is proposed. [17]In the Ge-S or Ge-Se system of metal chalcogenides tetrahedral molecular clusters, Feng's group found that clus‐ ters larger than T2 cannot be prepared in this system. The reason is that the charge at cation sites is too high to satisfy the coordination environment of 3-coordinated anion sites in clus‐ ters larger than T2. For the same reason, it is not surprise to find that no regular T3 cluster

, Mn2+) to join the metal chalcogenides tetrahedral mo‐

of one or more clusters, when crystallization involving these clusters occurs. [3]

**3.1. Chalcogenides with different valence state of metal cations**

can besuccessfully prepared in the pure Sn-S (or Sn-Se) system.

the oxides analogue. [3, 29]

410 Advanced Topics on Crystal Growth

mono- or divalent cations (e. g., Cu+

In oxides compounds, the oxygen sites of the anionic framework can form strong hydrogen bonding with N-H groups of protonated amine molecules. [3] Such O…H-N bonding is an important factor in the directed assembly of oxide frameworks. The hydrogen bonding be‐ tween chalcogenides frameworks and guest molecules (e. g., S…H-N) is very weak. [3]Based on the host–guest charge-density matching principle, proposed by Stucky et al., the content and distribution of heteroatoms in the framework can be adjusted by the guest species. [35] Thus, the co-assembly of metal chalcogenides tetrahedral molecular clusters with structuredirecting agent (guest), such as amine molecules, depends to a large extent on the host-guest electrostatic interaction. This principle can explain that open framework metal chalcoge‐ nides tetrahedral molecular generally have a rather negative framework and few neutral or nearly neutral open framework metal chalcogenides tetrahedral molecular are known today.

Interestingly, Yang et al. employ 4,4-trimethylene dipiperidine (TMDP), and histidine as the structure-directing agents for the synthesis of compound with mixed supertetrahedralchalco‐ genide clusters T2, and pentasupertetrahedralchalcogenide clusters P1, denoted as NCYU-5, (NCYUis named after National Chia Yi University), shown in Figure 6. [36]The TMDP is widely used as a structure construction template in the synthesis of T*n* series chalcogenide clusters. [37] However, the use of amino acid in the hydrothermal synthesis for an inorganic tetrahedral cluster has not been reported. In this case, the porosity of the mixed chalcogenide clusters with a TMDP only template is about 55%, smaller than the one with TMDP and histi‐ dine as templates. On the basis of experimental data, the role of histidine in the formation of mixed chalcogenide clusters is to improve the pore size of the 2-D framework, and the porosi‐ ty of the crystal. The potential cavity occupied 67. 1% of crystal cell volume can be calculated by the PLATON program. (a collection tool for single crystal structure analysis). The high per‐ centage of cavity derived from NCYU-5 suggests that large amount of guest molecules, i. e. TMDP, and histidine, present in the structure of open frame work to make this material with high porosity. In each layer of the two dimensional open frame work of NCYU-5, alternating P1 and T2 clusters are linked together by bridging selenium atoms, Fig. 7(a). A triangle-shap‐ ed pore window is created by three T2 clusters, three P1 clusters, and six bridging Se atoms. The distance between the two corner Se atoms of the triangle-shaped window is 18. 467(3) Å2 , and the theoretical area of a triangle-shaped pore window is 147. 6 Å2 , Fig. 7(b). The T2 clus‐ ters in one layer are located above or below the center of the 15-ring-window of its adjacent layers. The orientation of these T2 clusters is consistent. Although, these two-dimensional lay‐ ers are stacked along the c-axis, the P1 clusters are located above or below P1 clusters of the adjacent layers with skewed orientation, Fig. 7(c). [36]

**Figure 7.** a) The 2-D open frame work of NCYU-5, alternating P1 and T2 clusters are linked together by bridging Se atoms. (b) The distance between the two corner Se atoms of the triangle-shaped window is 18. 467 Å2. The theoretical

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In the past decades, numerous metal chalcogenides tetrahedral molecular clusters have been successfully prepared. Although, these metal chalcogenides solids posses a wide range of compositions and topological features, the application potential is limited by the low thermal stability of these compounds. Up to present, not many metal chalcogenides tetrahedral molecular clusters can maintain the thermal stability in500℃ or higher, which is a required temperature to completely remove organic guest molecules through calcina‐ tions. [3]One example that can achieve the requirement is NCYU-5 that can maintain the crystal structure from room temperature (RT) to 505 °C.. The thermogravimetric analysis (TGA) data of NCYU-5 is given in Figure 8. [36]The total weight loss is 26. 72% from RT to 505 °C. The initial weight loss of 3. 09% from RT to 110 °C is because of the water desorp‐ tion of surface. A sharp weight loss of 10. 46% starting from 305 °C to 405 °C is attributed by the decomposition of two histidine molecules (calcd. 11. 5%). The second sharp weight loss of 13. 17% observed from 405 °C to 505 °C is possibly contributed by the decomposi‐ tion of two TMDP molecules and the removal of H2S (calcd. 15. 6%). No further weight loss is observed after 505 °C. The total recorded weight loss of 26. 72% from 105 °C to 505 °C is in good agreement with the calculated weight loss (27. 1%) for the guest molecules, i. e. one TMDP and one histidine in each unit cell of NCYU-5. As for the direct calcination of assynthesized samples by suitable temperature to remove a sizable fraction of extra-frame work organic components is shown in another example. In Feng et al. 's reported, ~77% of nitrogen and ~81% of hydrogen were removed from UCR-20GaGeS-TAEA, (TAEA = tris(2 aminoethyl)amine, UCR= initials of University of California Riverside), by direct calcina‐ tion at 350 °C with nitrogen gas. [34] However, the coke formation made the removal of carbon difficult, only ~39% of carbon was removed from UCR-20GaGeS-TAEA in the same

area of a triangle-shaped pore window is 147. 6 Å2. (c) Two adjacent layers stacked along c-axis. [36]

**3.3. Selected properties of metal chalcogenides tetrahedral molecular clusters**

*3.3.1. Thermal characteristics*

experiment. [34]

**Figure 6.** An illustrated unit cell structure for NCYU-5. The calculated occupancy possibility of the Se(1) site for Se to S is ~90%. The occupancy possibility of the S3 site in the T2 cluster for Se to S is ~10%. [36]

**Figure 7.** a) The 2-D open frame work of NCYU-5, alternating P1 and T2 clusters are linked together by bridging Se atoms. (b) The distance between the two corner Se atoms of the triangle-shaped window is 18. 467 Å2. The theoretical area of a triangle-shaped pore window is 147. 6 Å2. (c) Two adjacent layers stacked along c-axis. [36]

#### **3.3. Selected properties of metal chalcogenides tetrahedral molecular clusters**

#### *3.3.1. Thermal characteristics*

,

, Fig. 7(b). The T2 clus‐

electrostatic interaction. This principle can explain that open framework metal chalcoge‐ nides tetrahedral molecular generally have a rather negative framework and few neutral or nearly neutral open framework metal chalcogenides tetrahedral molecular are known today.

Interestingly, Yang et al. employ 4,4-trimethylene dipiperidine (TMDP), and histidine as the structure-directing agents for the synthesis of compound with mixed supertetrahedralchalco‐ genide clusters T2, and pentasupertetrahedralchalcogenide clusters P1, denoted as NCYU-5, (NCYUis named after National Chia Yi University), shown in Figure 6. [36]The TMDP is widely used as a structure construction template in the synthesis of T*n* series chalcogenide clusters. [37] However, the use of amino acid in the hydrothermal synthesis for an inorganic tetrahedral cluster has not been reported. In this case, the porosity of the mixed chalcogenide clusters with a TMDP only template is about 55%, smaller than the one with TMDP and histi‐ dine as templates. On the basis of experimental data, the role of histidine in the formation of mixed chalcogenide clusters is to improve the pore size of the 2-D framework, and the porosi‐ ty of the crystal. The potential cavity occupied 67. 1% of crystal cell volume can be calculated by the PLATON program. (a collection tool for single crystal structure analysis). The high per‐ centage of cavity derived from NCYU-5 suggests that large amount of guest molecules, i. e. TMDP, and histidine, present in the structure of open frame work to make this material with high porosity. In each layer of the two dimensional open frame work of NCYU-5, alternating P1 and T2 clusters are linked together by bridging selenium atoms, Fig. 7(a). A triangle-shap‐ ed pore window is created by three T2 clusters, three P1 clusters, and six bridging Se atoms. The distance between the two corner Se atoms of the triangle-shaped window is 18. 467(3) Å2

ters in one layer are located above or below the center of the 15-ring-window of its adjacent layers. The orientation of these T2 clusters is consistent. Although, these two-dimensional lay‐ ers are stacked along the c-axis, the P1 clusters are located above or below P1 clusters of the

**Figure 6.** An illustrated unit cell structure for NCYU-5. The calculated occupancy possibility of the Se(1) site for Se to S

is ~90%. The occupancy possibility of the S3 site in the T2 cluster for Se to S is ~10%. [36]

and the theoretical area of a triangle-shaped pore window is 147. 6 Å2

adjacent layers with skewed orientation, Fig. 7(c). [36]

412 Advanced Topics on Crystal Growth

In the past decades, numerous metal chalcogenides tetrahedral molecular clusters have been successfully prepared. Although, these metal chalcogenides solids posses a wide range of compositions and topological features, the application potential is limited by the low thermal stability of these compounds. Up to present, not many metal chalcogenides tetrahedral molecular clusters can maintain the thermal stability in500℃ or higher, which is a required temperature to completely remove organic guest molecules through calcina‐ tions. [3]One example that can achieve the requirement is NCYU-5 that can maintain the crystal structure from room temperature (RT) to 505 °C.. The thermogravimetric analysis (TGA) data of NCYU-5 is given in Figure 8. [36]The total weight loss is 26. 72% from RT to 505 °C. The initial weight loss of 3. 09% from RT to 110 °C is because of the water desorp‐ tion of surface. A sharp weight loss of 10. 46% starting from 305 °C to 405 °C is attributed by the decomposition of two histidine molecules (calcd. 11. 5%). The second sharp weight loss of 13. 17% observed from 405 °C to 505 °C is possibly contributed by the decomposi‐ tion of two TMDP molecules and the removal of H2S (calcd. 15. 6%). No further weight loss is observed after 505 °C. The total recorded weight loss of 26. 72% from 105 °C to 505 °C is in good agreement with the calculated weight loss (27. 1%) for the guest molecules, i. e. one TMDP and one histidine in each unit cell of NCYU-5. As for the direct calcination of assynthesized samples by suitable temperature to remove a sizable fraction of extra-frame work organic components is shown in another example. In Feng et al. 's reported, ~77% of nitrogen and ~81% of hydrogen were removed from UCR-20GaGeS-TAEA, (TAEA = tris(2 aminoethyl)amine, UCR= initials of University of California Riverside), by direct calcina‐ tion at 350 °C with nitrogen gas. [34] However, the coke formation made the removal of carbon difficult, only ~39% of carbon was removed from UCR-20GaGeS-TAEA in the same experiment. [34]

Open-framework metal chalcogenides tetrahedral molecular clusters are anticipated as bet‐ ter ion conductors than zeolites. The chalcogenides have higher anionic framework polariza‐ bility created by the large size of S2- or Se2-, as compared with O2-. [1]The high polarizable anionic framework will facilitate the migration of mobile cations quick. Since the concentra‐ tion of mobile cations is high in the open-framework metal chalcogenides tetrahedral molec‐ ular clusters. The chalcogenides clusters will have more negative frameworks for chargebalane than that of zeolites. The experimental data show that the framework M4+/M3+ (where M is a tetrahedral atom) ratio in chalcogenides is smaller than one, whereas the ratio value is always larger or equal to one in zeolites or related oxides. [3]For example, the synthesis of hydrated sulphides and selenides with highly mobile alkali or alkaline earth metal cations as extra framework cations, such as ICF-26. [3,22] The ionic conductivity of ICF-26 (Figure 10) is comparable to or exceeds previously known crystalline sodium or lithium conductors at RT and under relative humidity of 30% or higher. The highest specific conductivity ach‐ ieved among open framework chalcogenides is 0. 15 Ω-1 cm-1 at 27 °C and under 100% rela‐

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**Figure 9.** Nitrogen adsorption and desorption isotherms measured at 77 K for the Cs+ exchanged UCR-20GaGeSTAEA.

tive humidity. [3,40]

[34]

**Figure 8.** TGA data of NCYU-5. The total weight loss is 26. 72% from RT to 800 °C. [36]

#### *3.3.2. Ion exchange*

Ion exchange is the most common properties of open framework solids. [38] This proper‐ ty has been shown for a number of metal chalcogenides tetrahedral molecular clusters, in which the protonated guests can be exchanged in solution by inorganic monocations (i. e., Li+ , Na+ , K+ , Rb+ , Cs+ ) and dications (i. e., Mg2+, Ca2+, Sr2+, Ba2+). After ion-exchange, micro‐ porosity of compound can be created by the removal of large organic cations. [34,39] For example, the ion-exchange with Cs+ ions led to an almost complete removal of amine mol‐ ecules from UCR-20GaGeS-TAEA. The Cs+ -exchanged UCR-20GaGeS-TAEA exhibits the type I isotherm characteristic of a microporous solid (Figure 9). This sample has a high BET surface area (807 m2 /g) and a micropore volume (0. 23 cm3 /g) despite the presence of much heavier elements (i. e., Cs, Ga, Ge, and S), compared with the analogues of alumino‐ silicate zeolites. [34]

#### *3.3.3. Conductivity*

An open-framework material has an inherent advantage for the applications in low-temper‐ ature fast-ion conductors. The existed open channels in these compounds provide the neces‐ sary paths for ions migration. Unfortunately, the sizeable open channels and cages contained in zeolites are not good fast-ion conductors because of the strong interaction be‐ tween the oxygen framework and extra-framework charge carriers, such as Li+ and Na+ . [38]

Open-framework metal chalcogenides tetrahedral molecular clusters are anticipated as bet‐ ter ion conductors than zeolites. The chalcogenides have higher anionic framework polariza‐ bility created by the large size of S2- or Se2-, as compared with O2-. [1]The high polarizable anionic framework will facilitate the migration of mobile cations quick. Since the concentra‐ tion of mobile cations is high in the open-framework metal chalcogenides tetrahedral molec‐ ular clusters. The chalcogenides clusters will have more negative frameworks for chargebalane than that of zeolites. The experimental data show that the framework M4+/M3+ (where M is a tetrahedral atom) ratio in chalcogenides is smaller than one, whereas the ratio value is always larger or equal to one in zeolites or related oxides. [3]For example, the synthesis of hydrated sulphides and selenides with highly mobile alkali or alkaline earth metal cations as extra framework cations, such as ICF-26. [3,22] The ionic conductivity of ICF-26 (Figure 10) is comparable to or exceeds previously known crystalline sodium or lithium conductors at RT and under relative humidity of 30% or higher. The highest specific conductivity ach‐ ieved among open framework chalcogenides is 0. 15 Ω-1 cm-1 at 27 °C and under 100% rela‐ tive humidity. [3,40]

**Figure 8.** TGA data of NCYU-5. The total weight loss is 26. 72% from RT to 800 °C. [36]

ecules from UCR-20GaGeS-TAEA. The Cs+

Ion exchange is the most common properties of open framework solids. [38] This proper‐ ty has been shown for a number of metal chalcogenides tetrahedral molecular clusters, in which the protonated guests can be exchanged in solution by inorganic monocations (i. e.,

porosity of compound can be created by the removal of large organic cations. [34,39] For example, the ion-exchange with Cs+ ions led to an almost complete removal of amine mol‐

type I isotherm characteristic of a microporous solid (Figure 9). This sample has a high

much heavier elements (i. e., Cs, Ga, Ge, and S), compared with the analogues of alumino‐

An open-framework material has an inherent advantage for the applications in low-temper‐ ature fast-ion conductors. The existed open channels in these compounds provide the neces‐ sary paths for ions migration. Unfortunately, the sizeable open channels and cages contained in zeolites are not good fast-ion conductors because of the strong interaction be‐

tween the oxygen framework and extra-framework charge carriers, such as Li+

/g) and a micropore volume (0. 23 cm3

) and dications (i. e., Mg2+, Ca2+, Sr2+, Ba2+). After ion-exchange, micro‐


/g) despite the presence of

and Na+

. [38]

*3.3.2. Ion exchange*

414 Advanced Topics on Crystal Growth

BET surface area (807 m2

silicate zeolites. [34]

*3.3.3. Conductivity*

Li+ , Na+ , K+ , Rb+ , Cs+

**Figure 9.** Nitrogen adsorption and desorption isotherms measured at 77 K for the Cs+ exchanged UCR-20GaGeSTAEA. [34]

**Figure 10.** The ionic conductivity of ICF-26 under different relative humidity. Ionic conductivities were measured on a single crystal (cross section 0. 37 x 0. 43 mm2, length 0. 63 mm). [3]

**Figure 11.** The RT PL spectra for NCYU-T3 family. Two emission peaks, centered at about 457 nm and 538 nm, were

or 4; M = Mn, Cu, Zn; Q = S, Se), prepared by Feng's group, show an unusual phase transfor‐ mation from a T4 covalent framework (3-D) into T4 molecular clusters (0-D), denoted as OCF-5s or OCF-40s (OCF stands for organically directed chalcogenide frameworks). In the case of OCF-40s, these iso-structural compounds show a remarkable effect of different d10

gap of semiconductor materials. The UV–vis diffuse reflectance spectrum reveals that the dark red selenide sample of OCF-40-CuGaSnSe-PR (formula:[Cu2Ga16Sn2Se35] 12(C5NH12), PR = piperidine) has a wider UV-vis adsorption peak thanthe yellow sample of OCF-40- ZnGaSnSe-PR. (formula:[Zn4Ga14Sn2Se35] 12(C5NH12)). A similar difference is also found in sulfides analogues between OCF-40-CuGaSnS-PR (formula:[Cu2Ga16Sn2S35] 12(C5NH12)) and OCF-40-ZnGaSnS-PR. (formula:[Zn4Ga14Sn2S35] 12(C5NH12)). The solid-state diffuse reflec‐ tance spectra, shown in Figure 12,show that OCF-40s are semiconductors with different band gaps(bg): OCF-40-CuGaSnSe-PR, bg = 1. 91 eV; OCF-40-ZnGaSnSe-PR, bg = 2. 71 eV; OCF-40-CuGaSnS-PR, bg = 2. 11 eV; and OCF-40-ZnGaSnS-PR, bg = 3. 59 eV. The experi‐

mental data show that metal chalcogenides tetrahedral molecular clusters with Cu+

in the framework will have much lower band gaps. [45]

and Zn2+) and chalcogen anions(Se2- and S2-) on the sample colors and band

Metal Chalcogenides Tetrahedral Molecular Clusters: Crystal Engineering and Properties

http://dx.doi.org/10. 5772/52660

417

12-[45] (x = 2

and Se2-

On the other hand, a family of discrete chalcogenide T4 clusters [MxGa18-xSn2Q35]

revealed from the NCYU-3. [44]

metal ions (Cu+

### *3.3.4. Optical properties*

Most open framework chalcogenides without the incorporation with organic dyes or met‐ al activators still can display photoluminescence with tunable emission wavelengths rang‐ ing almost continuously from 450 to 600nm. [41]The luminescence of open framework chalcogenidesis known to be related with the highly negatively charged inorganic frame‐ work and the presence of protonated guest amine molecules. [41, 42]On the top of this re‐ view point, Se exhibits a better induced optoelectronic property than S because the ionization energy barrier of Se is much lower than that of S. [36, 43, 44] Based on this un‐ derstanding, Yang et al. prepared the Se doped metal chalcogenides tetrahedral molecular clusters, i. e. NCYU family, to study the optoelectronic luminescent phenomena induced by the quantum confinement of Se in these clusters. The clusters prepared by Yang's group include NCYU-1 (T4/Se), NCYU-3 (T3/Se), and NCYU-5 (mixed P1+T2/Se). [36, 43, 44]Two PL emission peaks, centered at about 457 nm and 538 nm, were revealed from the NCYU-3(T3/Se). But only the 457 nm peak is observed in the spectra of NCYU-InS-AEAE (T3)(AEAE= 2-(2-aminoethylamino)ethanol) and NCYU-4 (T3). The peak at 457 nm has been reported for the luminescence of open framework chalcogenides. Thus, the trace Se atoms confined in the NCYU-3 (T3/Se) supertetrahedral clusters is responsible for the newly discovered 538 nm emission peak (Figure 11). [44]

**Figure 11.** The RT PL spectra for NCYU-T3 family. Two emission peaks, centered at about 457 nm and 538 nm, were revealed from the NCYU-3. [44]

**Figure 10.** The ionic conductivity of ICF-26 under different relative humidity. Ionic conductivities were measured on a

Most open framework chalcogenides without the incorporation with organic dyes or met‐ al activators still can display photoluminescence with tunable emission wavelengths rang‐ ing almost continuously from 450 to 600nm. [41]The luminescence of open framework chalcogenidesis known to be related with the highly negatively charged inorganic frame‐ work and the presence of protonated guest amine molecules. [41, 42]On the top of this re‐ view point, Se exhibits a better induced optoelectronic property than S because the ionization energy barrier of Se is much lower than that of S. [36, 43, 44] Based on this un‐ derstanding, Yang et al. prepared the Se doped metal chalcogenides tetrahedral molecular clusters, i. e. NCYU family, to study the optoelectronic luminescent phenomena induced by the quantum confinement of Se in these clusters. The clusters prepared by Yang's group include NCYU-1 (T4/Se), NCYU-3 (T3/Se), and NCYU-5 (mixed P1+T2/Se). [36, 43, 44]Two PL emission peaks, centered at about 457 nm and 538 nm, were revealed from the NCYU-3(T3/Se). But only the 457 nm peak is observed in the spectra of NCYU-InS-AEAE (T3)(AEAE= 2-(2-aminoethylamino)ethanol) and NCYU-4 (T3). The peak at 457 nm has been reported for the luminescence of open framework chalcogenides. Thus, the trace Se atoms confined in the NCYU-3 (T3/Se) supertetrahedral clusters is responsible for the

single crystal (cross section 0. 37 x 0. 43 mm2, length 0. 63 mm). [3]

newly discovered 538 nm emission peak (Figure 11). [44]

*3.3.4. Optical properties*

416 Advanced Topics on Crystal Growth

On the other hand, a family of discrete chalcogenide T4 clusters [MxGa18-xSn2Q35] 12-[45] (x = 2 or 4; M = Mn, Cu, Zn; Q = S, Se), prepared by Feng's group, show an unusual phase transfor‐ mation from a T4 covalent framework (3-D) into T4 molecular clusters (0-D), denoted as OCF-5s or OCF-40s (OCF stands for organically directed chalcogenide frameworks). In the case of OCF-40s, these iso-structural compounds show a remarkable effect of different d10 metal ions (Cu+ and Zn2+) and chalcogen anions(Se2- and S2-) on the sample colors and band gap of semiconductor materials. The UV–vis diffuse reflectance spectrum reveals that the dark red selenide sample of OCF-40-CuGaSnSe-PR (formula:[Cu2Ga16Sn2Se35] 12(C5NH12), PR = piperidine) has a wider UV-vis adsorption peak thanthe yellow sample of OCF-40- ZnGaSnSe-PR. (formula:[Zn4Ga14Sn2Se35] 12(C5NH12)). A similar difference is also found in sulfides analogues between OCF-40-CuGaSnS-PR (formula:[Cu2Ga16Sn2S35] 12(C5NH12)) and OCF-40-ZnGaSnS-PR. (formula:[Zn4Ga14Sn2S35] 12(C5NH12)). The solid-state diffuse reflec‐ tance spectra, shown in Figure 12,show that OCF-40s are semiconductors with different band gaps(bg): OCF-40-CuGaSnSe-PR, bg = 1. 91 eV; OCF-40-ZnGaSnSe-PR, bg = 2. 71 eV; OCF-40-CuGaSnS-PR, bg = 2. 11 eV; and OCF-40-ZnGaSnS-PR, bg = 3. 59 eV. The experi‐ mental data show that metal chalcogenides tetrahedral molecular clusters with Cu+ and Se2 in the framework will have much lower band gaps. [45]

**Figure 12.** Effects of Cu+vs Zn2+ and Se2-vs S2- on band structures in solid state: normalized solid-state UV-vis absorp‐ tion spectra of OCF-40s. Insets are photos of the as-synthesized crystalline materials. [45]

**Figure 13.** Photocatalytic H2 evolution from an aqueous solution ofNa2S (0. 5M) over ICF-5 CuInS-Na (0. 5 g); t: irradia‐

Metal Chalcogenides Tetrahedral Molecular Clusters: Crystal Engineering and Properties

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419

[1] Sokolov, M. N. Metal Chalcogenides. In *Handbook of Chalcogen Chemistry: New Per‐ spectives in Sulfur, Selenium and Tellurium*; Devillanova, F. A.; Royal Society of Chem‐

[2] Férey, G. Supertetrahedra in Sulfides: Matter against mathematical series? *Angew.*

[3] Feng, P.; Bu, X.; Zheng, N. The Interface Chemistry between Chalcogenide Clusters

[4] Li, H.; Laine, A.; O'Keeffe, M.; Yaghi, O. M. Supertetrahedral sulfide crystals with

and Open Framework Chalcogenides. *Acc. Chem. Res.* 2005, 38, 293-303.

giant cavities and channels. *Science* 1999, 283, 1145-1147.

tion time, n:amount of H2. [46]

Chun-Chang Ou and Chung-Sung Yang\*

istry: Cambridge U.K., 2007; p543.

*Chem., Int. Ed.* 2003, 42, 2576-257.

\*Address all correspondence to: csyang@mail. ncyu. edu. tw

Department of Applied Chemistry, National Chia Yi University, Taiwan, ROC

**Author details**

**References**

#### *3.3.5. Photocatalytic applications*

Over the past few decades, a large family of crystalline porous materials based on metal chalcogenides were developed. [3-7,36,43,44]These materials integrate tunable band gaps with an open-framework architecture and are potential candidates for efficient photocata‐ lysts due to their optical properties. By controlling framework architecture, it is possible to tune the band structure (both band positions and gap) of an open-framework solid within a given compositional domain. The open-framework construction can increase the number of active reaction sites by the high surface area. [46] In order to evaluate catalytic efficiency for hydrogen generation by metal chalcogenides tetrahedral molecular clusters, a series of po‐ rous crystalline open-framework sulfides, such as ICF-17MnInS-Na (formula: Na16- Mn13In22S54 xH2O) or ICF-5CdInS-Na (formula: Na10-Cd4In16S33 xH2O), are prepared by Feng's group. [46]Under the irradiation of visible light, ICF-5CdInS-Nais photocatalytically active without the use of a co-catalyst, such as Pt. As shown in Figure 13,about 18 mmolh-1g-1 of H2 gas was produced over the ICF-5CuInS-Na catalyst under irradiation with the visible light. This activity was maintained for over 96 h and more than890 mmol of H2 gas evolved dur‐ ing this period. The quantum efficiency for ICF-5CuInS-Na was about 3. 7% at 420 nm. Even though the number is lower than the quantum yield(~35%) of the well-known Pt/CdS photo‐ catalyst, the efficiency is a considerable improvement on two anhydrous dense phases with similar compositions: CuInS2 with the cubic ZnS structure, and CuIn5S8 with the spinel structure.

Metal Chalcogenides Tetrahedral Molecular Clusters: Crystal Engineering and Properties http://dx.doi.org/10. 5772/52660 419

**Figure 13.** Photocatalytic H2 evolution from an aqueous solution ofNa2S (0. 5M) over ICF-5 CuInS-Na (0. 5 g); t: irradia‐ tion time, n:amount of H2. [46]

### **Author details**

**Figure 12.** Effects of Cu+vs Zn2+ and Se2-vs S2- on band structures in solid state: normalized solid-state UV-vis absorp‐

Over the past few decades, a large family of crystalline porous materials based on metal chalcogenides were developed. [3-7,36,43,44]These materials integrate tunable band gaps with an open-framework architecture and are potential candidates for efficient photocata‐ lysts due to their optical properties. By controlling framework architecture, it is possible to tune the band structure (both band positions and gap) of an open-framework solid within a given compositional domain. The open-framework construction can increase the number of active reaction sites by the high surface area. [46] In order to evaluate catalytic efficiency for hydrogen generation by metal chalcogenides tetrahedral molecular clusters, a series of po‐ rous crystalline open-framework sulfides, such as ICF-17MnInS-Na (formula: Na16- Mn13In22S54 xH2O) or ICF-5CdInS-Na (formula: Na10-Cd4In16S33 xH2O), are prepared by Feng's group. [46]Under the irradiation of visible light, ICF-5CdInS-Nais photocatalytically active without the use of a co-catalyst, such as Pt. As shown in Figure 13,about 18 mmolh-1g-1 of H2 gas was produced over the ICF-5CuInS-Na catalyst under irradiation with the visible light. This activity was maintained for over 96 h and more than890 mmol of H2 gas evolved dur‐ ing this period. The quantum efficiency for ICF-5CuInS-Na was about 3. 7% at 420 nm. Even though the number is lower than the quantum yield(~35%) of the well-known Pt/CdS photo‐ catalyst, the efficiency is a considerable improvement on two anhydrous dense phases with similar compositions: CuInS2 with the cubic ZnS structure, and CuIn5S8 with the spinel

tion spectra of OCF-40s. Insets are photos of the as-synthesized crystalline materials. [45]

*3.3.5. Photocatalytic applications*

418 Advanced Topics on Crystal Growth

structure.

Chun-Chang Ou and Chung-Sung Yang\*

\*Address all correspondence to: csyang@mail. ncyu. edu. tw

Department of Applied Chemistry, National Chia Yi University, Taiwan, ROC

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## *Edited by Sukarno Olavo Ferreira*

Crystal growth is the key step of a great number of very important applications. The development of new devices and products, from the traditional microelectronic industry to pharmaceutical industry and many others, depends on crystallization processes. The objective of this book is not to cover all areas of crystal growth but just present, as specified in the title, important selected topics, as applied to organic and inorganic systems. All authors have been selected for being key researchers in their field of specialization, working in important universities and research labs around the world. The first section is mainly devoted to biological systems and covers topics like proteins, bone and ice crystallization. The second section brings some applications to inorganic systems and describes more general growth techniques like chemical vapor crystallization and electrodeposition. This book is mostly recommended for students working in the field of crystal growth and for scientists and engineers in the fields of crystalline materials, crystal engineering and the industrial applications of crystallization processes.

Advanced Topics on Crystal Growth

Advanced Topics on

Crystal Growth

*Edited by Sukarno Olavo Ferreira*

Photo by wacomka / iStock