Skip to Main Content
Skip Nav Destination

Carbonyl chalcogenide metal coordination polymers have drawn much attention in recent decades owing to their fascinating structures, variable bonding modes, and potential applications in material science. While most polymers were constructed by transition metal carbonyls that were further linked by chalcogen atoms or chalcogen-containing ligands, some polymers were built from predesigned chalcogen-containing metal carbonyl clusters that were bridged by organic or inorganic ligands. The significant interactions between electronegative chalcogens and electropositive metal carbonyls along with variable non-classical weak interactions within the frameworks were found to enhance the stability of the resultant supramolecules and polymers under ambient conditions. In addition to some representative metal carbonyl chalcogenide polymers, this chapter will mainly cover carbonyl chalcogenide cluster-based supramolecules and polymers from groups 6 to 8 metals in terms of syntheses, structural features, and their potential applications in the fields of semiconductors, photodegradation, magnetism, catalysis, and adsorption/desorption.

In the modern era, coordination polymers have gained a lot of attention from chemists and materials scientists owing to their versatile structures and topologies, unusual physical and chemical properties, and a wide range of applications as sensing, catalytic, and semiconducting materials.1–3  These coordination frameworks usually consisted of main-group element-containing ligands that coordinated to more electropositive metal atoms, complexes, or clusters, leading to the formation of various coordination polymers.1  Despite the most used pnictogenides as bridging ligands, the chalcogenides (O, S, Se, and Te) could also bind to metal fragments to produce chalcogen–metal coordination polymers.2  The strong coupling effect of the heavier chalcogens (S, Se, and Te) and transition metals usually resulted in versatile structures with unique magnetic or electrical properties.2a 

The introduction of metal clusters into polymeric frameworks was one of the challenging issues in the chemistry of coordination polymers.3  Metal clusters usually possess intrinsic physical and chemical properties, such as magnetic and semiconducting properties, which effectively make functionalized polymers suitable for use in materials science. Among them, metal carbonyl clusters have long been known as electron reservoirs, which could further modulate the electronic properties of the building units for the construction of multifunctional polymers.3d  Recent studies showed that introducing carbonyls into polymers could delicately give rise to numerous secondary interactions in the solid state that enhanced the stability and facilitated electron transport of their polymeric frameworks, making them potential semiconductors.3a  Given these intriguing facts, this chapter will mainly focus on the recent progress on carbonyl heavier chalcogenide cluster-based coordination polymers, ranging from group 6 to group 8 metals, covering the syntheses, structural features, and potential applications. Some representative metal carbonyl complexes will also be introduced as building units for polymeric frameworks.

Following a survey in the CCDC database, only a few group 6 metal carbonyl chalcogenide polymers were covered in this category. This section will discuss syntheses, structures, and some unique potential applications of several mono- or dinuclear group 6 metal carbonyl-containing polymers.

In 1981, Cooper and McPartlin et al. reported the syntheses and structural characterizations of SH-containing metal carbonyl complexes [Na(18-crown-6)][M(CO)5(SH)] and [Na(18-crown-6)][M2(CO)10(SH)] (M = Cr, Mo, W). These complexes could be obtained from UV irradiations of M(CO)6, Na2S, and 18-crown-6 in ethanol at ambient temperature.4  Compared to cations [Et4N]+ used as counterions, the bulky cations [Na(18-crown-6)]+ enhanced the stability of these complexes in the solid state. X-ray structural analysis of the tungsten analogues, [Na(18-crown-6)][W(CO)5(SH)] and [Na(18-crown-6)][W2(CO)10(SH)], showed that anions [W(CO)5(SH)] and [W2(CO)10(SH)] were each further linked by the cation [Na(18-crown-6)]+via Na–O(carbonyl) bonds to form 1D polymeric chains (Figure 1.1a and b). This type of tight Na–O(carbonyl) ion-pairing led to stabilization of the unstable metal carbonyl clusters and to the construction of infinite supramolecular frameworks.

Figure 1.1

A portion of (a) [Na(18-crown-6)][W(CO)5(SH)] (ref. code NACRWA), (b) [Na(18-crown-6)][W2(CO)10(SH)] (NACRWB), (c) [Bi(SCN){Mo(CO)3(Cp)}2]n (WETRAO), (d) [Zn(tbtp-dach)W(CO)5]n (RULXIG), and (e) cyclo-[{2-(2′,6′-iPr2C6H3NCH)C6H4}SbS]2[W(CO)5] (EPOCIX). Bright-blue, bright-green, yellow, pink, and orange dashed lines represent Bi⋯N, Zn⋯O, O⋯H, C–H⋯π, and S⋯H interactions, respectively.

Figure 1.1

A portion of (a) [Na(18-crown-6)][W(CO)5(SH)] (ref. code NACRWA), (b) [Na(18-crown-6)][W2(CO)10(SH)] (NACRWB), (c) [Bi(SCN){Mo(CO)3(Cp)}2]n (WETRAO), (d) [Zn(tbtp-dach)W(CO)5]n (RULXIG), and (e) cyclo-[{2-(2′,6′-iPr2C6H3NCH)C6H4}SbS]2[W(CO)5] (EPOCIX). Bright-blue, bright-green, yellow, pink, and orange dashed lines represent Bi⋯N, Zn⋯O, O⋯H, C–H⋯π, and S⋯H interactions, respectively.

Close modal

In addition, the SCN-containing Bi–Mo carbonyl polymer [Bi(SCN){Mo(CO)3(Cp)}2]n was synthesized from the reaction of Bi(SCN)3 with two equiv. of K[Mo(CO)3(Cp)] in THF solution.5  The X-ray analysis showed that [Bi(SCN){Mo(CO)3(Cp)}2]n contained a linear polymeric array built through intermolecular Bi⋯NCS–Bi interactions (Figure 1.1c). The Lewis-acidic bismuth centre and the Lewis-basic nitrogen of the thiocyanate ligand provided a good Lewis acid–base interaction to form the polymeric framework. The zinc-containing mono-thiolate-bridged tungsten carbonyl polymer [Zn(tbtp-dach)W(CO)5]n (tbtp-dach = N-(3-thiabutyl)-N′-(3-thiapentanoate)-1,4-diazacycloheptane) was obtained from the reaction of the S-donor metallo-ligand Zn(tbtp-dach) with (THF)W(CO)5.6  The [Zn(tbtp-dach)W(CO)5] molecules were connected together by intermolecular Zn⋯O(carboxylate) interactions to form the W(CO)5-decorating [Zn(tbtp-dach)]n zig–zag chain (Figure 1.1d). The strong attraction of the Zn⋯O(carboxylate) interaction was attributed to the formation of the (CO)5W–thiolate bond that reduced the electron-donating character of the thiolate and enhanced the electrophilicity of the Zn atom. In addition, the organoantimony-bridged S–W carbonyl complex, cyclo-[{2-(2,6-iPr2C6H3NCH)C6H4}SbS]2[W(CO)5], was synthesized from the reaction of the heterocyclic sulfide, cyclo-[{2-(2,6-iPr2C6H3NCH)C6H4}SbS]2, with [W(CO)5(THF)] in a 1 : 1 molar ratio.7  The dimeric units of the S–Sb–W compound were formed via weak S–H and C–H⋯π(Phcentroid) contacts. These dimeric moieties were further linked through intermolecular O⋯H and C–H⋯π(Phcentroid) interactions to give a polymeric structure (Figure 1.1e).

Several group 7 metal carbonyl chalcogenide polymers and supramolecules were documented in the CCDC database. Several paramagnetic and low-energy-gap semiconducting Mn telluride carbonyl supramolecules will be discussed. Some rhenium carbonyl compounds with rectangular geometry showed unique host–guest chemistry in the solid state.

Recently, a new series of small- to medium- to large-sized manganese telluride carbonyl clusters have been synthesized. They were obtained from the facile one-pot reaction of Mn2(CO)10 and Te powder with various metathesis trapping reagents (Et4NBr, TMBACl, PPNCl) in different molar ratios, temperatures, and concentrations of the base. These one-pot reactions led to the formation of a mono spirocyclic [TMBA]2[Mn4Te(CO)16], four-membered ring [TMBA]2[Mn2Te2(CO)8], hydride-containing square pyramidal [PPN]2[HMn3Te2(CO)9], and dumbbell-shaped [Et4N]4[Mn6Te6(CO)18] and [Et4N]4[Mn6Te10(CO)18] compounds (Scheme 1.1).8  It was worth noting that two large-sized, electron-precise clusters [Mn6Te6(CO)18]4− and [Mn6Te10(CO)18]4− possessed unusual paramagnetic properties with S = 1, derived from the presence of two types of Mn atoms in different oxidation states in the compounds. Their detailed magnetic properties will be further discussed in Section 1.5.3. In addition, interesting structural and spin-state transformations were revealed in these systems. It was found that the small-sized anions [Mn4Te(CO)16]2− and [Mn2Te2(CO)8]2− could convert into the larger anionic cluster [Mn6Te10(CO)18]4−. The reversible off/on magnetic-switched transformation between [HMn3Te2(CO)9]2− and [Mn6Te10(CO)18]4− was successfully achieved, and the magnetic transformation between the two anionic magnetic complexes [Mn6Te6(CO)18]4− and [Mn6Te10(CO)18]4− was also observed. These hexamanganese complexes represented the first examples of electron-precise paramagnetic manganese telluride carbonyl complexes. Furthermore, the hydride complex anion [HMn3Te2(CO)9]2− could undergo the reversible dehydridation/hydridation processes upon the treatment with HCl/NaBH4, and also could proceed with a reductive coupling to form the dimeric hydride complex [{HMn3Te2(CO)10}2]2− upon the addition of CO followed by O2.

Scheme 1.1

Synthesis and structural transformations of a series of Mn telluride complexes.

Scheme 1.1

Synthesis and structural transformations of a series of Mn telluride complexes.

Close modal

Importantly, X-ray structural analysis revealed that these Te–Mn anionic clusters were closely packed to each other, and their cations TMBA+, Et4N+, and PPN+ were further connected to the neighbouring anions via non-classical C–H⋯O(carbonyl) hydrogen bonds. Therefore, [TMBA]2[Mn4Te(CO)16] and [PPN]2[HMn3Te2(CO)9] could be extended to supramolecular 1D chains, while [TMBA]2[Mn2Te2(CO)8], [Et4N]4[Mn6Te6(CO)18], [Et4N]4[Mn6Te10(CO)18], and [PPN]2[{HMn3Te2(CO)10}2] formed supramolecular 2D sheets in the solid state (Figure 1.2). These 1D and 2D Te–Mn supramolecules possessed low-energy-gap semiconducting characteristics, which will be discussed in Section 1.5.1.

Figure 1.2

A portion of (a) an 1D chain in crystal [TMBA]2[Mn4Te(CO)16] (ref. code VUGKOA), (b) a 2D plane in crystal [TMBA]2[Mn2Te2(CO)8] (VUGKUG), (c) an 1D chain in crystal [Et4N]2[HMn3Te2(CO)9] (VUGLAN), (d) a 2D plane in crystal [Et4N]4[Mn6Te6(CO)18]·2MeCN (VUGLER), (e) a 2D plane in crystal [Et4N]4[Mn6Te10(CO)18] (VUGLIV), and (f) a 2D plane in crystal [PPN]2[{HMn3Te2(CO)10}2] (VUGLOB). Light-green dashed line represents the O⋯H interaction.

Figure 1.2

A portion of (a) an 1D chain in crystal [TMBA]2[Mn4Te(CO)16] (ref. code VUGKOA), (b) a 2D plane in crystal [TMBA]2[Mn2Te2(CO)8] (VUGKUG), (c) an 1D chain in crystal [Et4N]2[HMn3Te2(CO)9] (VUGLAN), (d) a 2D plane in crystal [Et4N]4[Mn6Te6(CO)18]·2MeCN (VUGLER), (e) a 2D plane in crystal [Et4N]4[Mn6Te10(CO)18] (VUGLIV), and (f) a 2D plane in crystal [PPN]2[{HMn3Te2(CO)10}2] (VUGLOB). Light-green dashed line represents the O⋯H interaction.

Close modal

Several representative cases of the Re carbonyl supramolecules and polymers are mentioned below. In 2006, the attractive thiolato-bridged Re(i) molecular rectangles, [{(SR)2Re2(CO)6}2(dpy)2] (R = C4H9, C8H17; dpy = 4,4′-dipyridyl), were obtained from the solvothermal reaction of Re2(CO)10, dpy, and respective alkyl thiol.9  These rectangles and their OR-substituted derivatives (R = C8H17, C12H25) showed good host–guest interactions toward the pyrene molecule and Ag+ ion upon the addition of pyrene or AgNO3, to give polymers [{(SC4H9)2Re2(CO)6}2(dpy)2(pyrene)]n and [{(SC4H9)2Re2(CO)6}2(dpy)2(AgNO3)2–(C3H6O)2}·C3H6O]n, respectively. The X-ray analysis of the pyrene-encapsulated polymer revealed that the two face-to-face dpy ligands interacted with pyrene via CH⋯π interactions to form a supramolecular stair-like array (Figure 1.3a). The S⋯Ag⋯ONO2 interaction was found in the framework for its Ag-intercalated polymer, giving a 1D supramolecular chain (Figure 1.3b). These rectangular complexes further revealed important Ag+- and pyrene-recognitions and absorptions properties, which will be described in detail in Section 1.5.5.

Figure 1.3

A portion of (a) [{(CO)3Re(SC4H9)2Re(CO)3}2(dpy)2(pyrene)]n (ref. code HEPLOE) and (b) [{(CO)3Re(SC4H9)2Re(CO)3}2(dpy)2(AgNO3)2(C3H6O)2}·C3H6O]n (HEPLUK). Light-green dashed line represents the O⋯H interaction.

Figure 1.3

A portion of (a) [{(CO)3Re(SC4H9)2Re(CO)3}2(dpy)2(pyrene)]n (ref. code HEPLOE) and (b) [{(CO)3Re(SC4H9)2Re(CO)3}2(dpy)2(AgNO3)2(C3H6O)2}·C3H6O]n (HEPLUK). Light-green dashed line represents the O⋯H interaction.

Close modal

In the group 8 metal system, many carbonyl chalcogenide polymers and supramolecules have been reported. The representative triiron carbonyl chalcogenide cluster anions [EFe3(CO)9]2− [E = Te (ATe); Se (ASe); S (AS)] were reported to readily react with metal salts either in the presence or in the absence of organic ligands. These reactions would form a series of coordination polymers or supramolecular frameworks. In addition, the di-copper-based compounds [EFe3(CO)9Cu2(MeCN)2] [E = Te (BTe); Se (BSe)] could also serve as predesigned building units to form a variety of coordination polymers via solution- or mechanochemical-based reaction. This section will describe the related syntheses and their fascinating structures.

The aryl sulfonate-bridged, di-thiolate-Fe2(CO)6-based complex, Na{(SCH2N(C6H4SO3)CH2S)}[Fe(CO)3]2, was synthesized from the reaction of (SH)2Fe2(CO)6 with sulfanilic acid and NaHCO3.10  This compound adopted an S2Fe2 butterfly geometry, with the CH2N(C6H4SO3)CH2 moiety coordinated to the two S atoms. The SO3 fragment of the CH2N(C6H4SO3)CH2 moiety was further connected to the Na+ ion via Na–O linkages, giving a 2D network. When an aqueous slurry of this di-thiolate iron complex was added to β-cyclodextrin (β-CyD), a di-β-CyD-hosted polymer, {Na{(SCH2N(C6H4SO3)CH2S)}[Fe(CO)3]2·2β-CyD}n, was obtained.10b  X-ray analysis showed that the polymer unit contained an S2Fe2 anionic guest cluster encapsulated by two host β-CyD moieties. The Na+ cations further connected these anionic host–guest units via Na–O interactions to form a 1D array. This novel β-CyD-hosted complex represented a model of a first-generation artificial protein with the [FeFe]-hydrogenase enzyme active site. Besides, the dinuclear iron(ii)–cyanocarbonyl polymer {[Na·2.5H2O][(µ-SEt)3Fe2(CO)4(CN)2]}n was obtained from the reaction of [PPN][Fe(CO)4(CN)] with I2 and Na(SEt).11  The anionic unit [(μ-SEt)3Fe2(CO)4(CN)2] was found to interact with the hydrated Na+ cations to create a polymeric framework via CN–Na linkages.

In 2008, the important Cu-linked Te–Fe polymers [{ATe}Cu]n and [{ATe}Cu2(dpy)1.5]n were obtained from the stoichiometric one-pot reaction of [TeFe3(CO)9]2− (ATe) and [Cu(MeCN)4]+ in the absence or in the presence of dpy in THF at 0 °C, respectively (Scheme 1.2).12  These two Te–Fe–Cu polymers could also be synthesized from the reactions of the neutral cluster compound TeFe3(CO)9Cu2(MeCN)2 (BTe) with 1 equiv. of [Et4N]2[ATe] or 1.5 equiv. of dpy in THF, respectively. Polymer [{ATe}Cu]n contained tetrahedral TeFe3 metal cores that were bridged by Cu+ ions across the Te–Fe edges, forming a 1D zig–zag chain (Figure 1.4a). The dpy-linked 1D polymer consisted of Cu-capped trigonal bipyramidal TeFe3(CO)9Cu2 units alternately linked by a single and a double dpy ligand bridge to give a 1D zig–zag-like framework (Figure 1.4b). The intramolecular π–π interactions were found between dpy linkers in the double bridge, implying efficient electron communications.

Scheme 1.2

Synthesis of the Te–Fe–Cu cluster-based polymers.

Scheme 1.2

Synthesis of the Te–Fe–Cu cluster-based polymers.

Close modal
Figure 1.4

A portion of (a) [{ATe}Cu]n (ref. code XOMSEY), (b) [{ATe}Cu2(dpy)1.5]n (XOMSIC), (c) [{ATe}Cu2bpee]n (WAYQOF), (d) [{ATe}Cu2L2.5]n (L = bpee, WAYRAS), (e) [{Cu2(bpp)4}({ATeCu}2bpp)]n (WAYRIA), and (f) [(AS)Cu2(dppe)(MeCN)2]n (PINTAJ). The H atoms in (e) were omitted for clarity.

Figure 1.4

A portion of (a) [{ATe}Cu]n (ref. code XOMSEY), (b) [{ATe}Cu2(dpy)1.5]n (XOMSIC), (c) [{ATe}Cu2bpee]n (WAYQOF), (d) [{ATe}Cu2L2.5]n (L = bpee, WAYRAS), (e) [{Cu2(bpp)4}({ATeCu}2bpp)]n (WAYRIA), and (f) [(AS)Cu2(dppe)(MeCN)2]n (PINTAJ). The H atoms in (e) were omitted for clarity.

Close modal

In 2017, a new family of 1D and 2D dipyridyl-bridged Te–Fe–Cu-based polymers were mechanochemically synthesized from the predesigned cluster BTe with a series of conjugated and conjugation-interrupted dipyridyl ligands (Scheme 1.2).13  Among them, the 1D zig–zag chains [{ATe}Cu2L]n (L = 1,2-bis(4-pyridyl)ethane (bpea), 1,2-bis(4-pyridyl)ethylene (bpee)), were found to be quantitatively synthesized via liquid-assisted grinding (LAG)14  of BTe with stoichiometric amounts of the corresponding dipyridyl ligands (Scheme 1.2).13  These 1D isostructural chain polymers, [{ATe}Cu2L]n (L = bpea, bpee), each contained the TeFe3(CO)9Cu2 units that were connected by two dipyridyl ligands via the Cu–N bonds to form the 1D zig–zag chain polymer (Figure 1.4c). Interestingly, these 1D [{ATe}Cu2L]n (L = bpea, bpee) polymers and the molecular cycle [{ATeCu2}2(bpp)2] (1,3-bis(4-pyridyl)propane (bpp)) could further react by grinding with the corresponding dipyridyl ligands to afford the 2D honeycomb-like polymers [{ATe}Cu2L2.5]n (L = bpea, bpee) and the 2D wave-like cation–anion polymer [{Cu2(bpp)4}({ATeCu}2bpp)]n in quantitative yields (Scheme 1.2).13  The 2D polymers, [{ATe}Cu2L2.5]n (L = bpea, bpee), are isostructural. They consisted of the tetrahedrally coordinated Cu nodes, each of which was bound to three bridging L (L = bpea or bpee) ligands and coordinated with one pendant TeFe3(CO)9Cu(L) ligand to give a honeycomb layer with (6,3) nets (Figure 1.4d). These 2D layers were closely stacked with pendant TeFe3(CO)9Cu(L) (L = bpea or bpee) fragments penetrating upward and downward to construct a 3D supramolecular framework via numerous C–H⋯O(carbonyl) contacts between COs and CH moieties of the dipyridyl linkers. Besides, the cation–anion polymer [{Cu2(bpp)4}({ATeCu}2bpp)]n contained a cationic (4,4) 2D net {[Cu2(bpp)4]2+}n and anionic bpp-bridged clusters [{ATeCu}2bpp]2−. These anionic clusters were intercalated between two cationic bilayers via several intermolecular interactions, i.e. aromatic C–H⋯π interactions and C–H⋯O(carbonyl) hydrogen bonds, giving a supramolecular 3D network (Figure 1.4e). These Te–Fe–Cu polymers exhibited semiconducting properties with narrow energy gaps,12,13  which will be mentioned in Section 1.5.1.

As far as S–Fe–Cu-based polymers are concerned, a bisphosphine-bridged SFe3(CO)9Cu2-based neutral cluster [(AS)Cu2dppe] was synthesized from the reaction of [SFe3(CO)9]2− (AS), [Cu(MeCN)4]+, and bis(diphenylphosphino)ethane (dppe) in CH2Cl2 (Scheme 1.3).15  Surprisingly, the polymeric complex [(AS)Cu2(dppe)(MeCN)2]n was readily produced when the neutral complex [(AS)Cu2dppe] was exposed to MeCN vapour (Scheme 1.3). X-ray analysis revealed that this dppe-linked polymer contained the AS cluster that was connected to the Cu(dppe)Cu(MeCN)2 moiety via Cu–Fe2 and S–Cu linkages, giving a 1D zig–zag chain (Figure 1.4f). The depolymerization of this polymer chain to the neutral cluster was successfully achieved via grinding with CH2Cl2 or THF.15  These results showed a novel solid-state transformation between the AS-based cluster and its 1D polymer via the rare vapor-diffusion-mediated and mechanochemical approaches.

Scheme 1.3

Synthesis and the reversible structural transformation of the dppe-linked S–Fe–Cu-based cluster and polymer.

Scheme 1.3

Synthesis and the reversible structural transformation of the dppe-linked S–Fe–Cu-based cluster and polymer.

Close modal

For the Se–Fe–Cu based polymers, a series of inorganic–organic hybrid Cu polymers were obtained via LAG of the three-components [Cu(MeCN)4]+, the inorganic anionic ligand [SeFe3(CO)9]2− (ASe), and the conjugated or conjugation-interrupted dipyridyl ligands.16  X-ray analysis showed that the ASe cluster units of these synthesized polymers were connected to the Cu atom by three distinct bonding patterns, cluster-linked, -blocked, and -pendant coordination modes. Hence, this series of new 1D and 2D polymers were classified based on their structural features as: cluster-linked 2D polymers [(μ4-ASe)Cu2(MeCN)(dpy)1.5]n and [(μ4-ASe)Cu2(bpp)2]n, cluster-blocked 1D polymers [(μ3-ASe)Cu2(L)]n (L = bpee, bpea), as well as the cluster-pendant 1D chain [(μ3-ASe)Cu2(dpy)3]n (Figure 1.5). Interestingly, reversible dimensionality transformations between 2D and 1D polymers accompanied by the change in the cluster bonding pattern were achieved by the LAG addition of the corresponding dipyridyls or ASe/[Cu(MeCN)4]+. Notably, the 2D dpy-connected cluster-linked polymer, [(μ4-ASe)Cu2(MeCN)(dpy)1.5]n, revealed a 5-fold interpenetrating 3D framework with numerous C–H⋯O(carbonyl) and C–H⋯π interactions in the solid state (Figure 1.5b).16  The relationship between these polymeric structures and their resulting properties, i.e. semiconducting and photodegradation properties, will be described in Sections 1.5.1 and 1.5.2.

Figure 1.5

A portion of (a) [(μ4-ASe)Cu2(bpp)2]n (ref. code SALJAU), (b) [(μ4-ASe)Cu2(MeCN)(dpy)1.5]n (SALHUM), and (c) [(μ3-ASe)Cu2(dpy)3]n (SALJEY). The H atoms and COs in (a) and (b) were omitted for clarity.

Figure 1.5

A portion of (a) [(μ4-ASe)Cu2(bpp)2]n (ref. code SALJAU), (b) [(μ4-ASe)Cu2(MeCN)(dpy)1.5]n (SALHUM), and (c) [(μ3-ASe)Cu2(dpy)3]n (SALJEY). The H atoms and COs in (a) and (b) were omitted for clarity.

Close modal

Furthermore, a series of N-heterocyclic carbene (NHC)-incorporated compounds [ASe{Cu(NHC)}2] (NHC = 1,3-dimethylimidazol-2-ylidene (Me2-imy), 1,3-dimethylbenzimidazol-2-ylidene (Me2-bimy), 1,3-diisopropylbenzimidazol-2-ylidene (iPr2-bimy), 1,3-dimethyl-4,5-dichloroimidazol-2-ylidene (Me2-Cl2-imy)), could be synthesized via one-pot stoichiometric reactions of [SeFe3(CO)9{Cu(MeCN)}2] (BSe), imidazolium salts, and KOtBu in THF.17  These NHC compounds contained the Cu2-ASe cores with the Cu atoms further coordinated by NHC ligands. In the solid state, their structures could be further extended into 1D chains (NHC = Me2-imy and Me2-bimy) or 2D frameworks (NHC = iPr2-bimy and Me2-Cl2-imy) through C–H⋯O(carbonyl) hydrogen bonds between CO groups and CH moieties of the NHC ligands. Surprisingly, these Se–Fe–Cu NHC compounds had catalytic activities for the homocoupling of arylboronic acids with high catalytic yields, which will be described in Section 1.5.4.

Recently, a rare class of mixed pnictogen (Bi and Sb) and chalcogen (Te, Se, or S) iron carbonyl clusters were systematically synthesized.18,19  In the case of the Bi system, when ATe or ASe was treated with BiCl3, square pyramidal anionic complexes [EBiFe3(CO)9] (E = Te, Se) were obtained (Scheme 1.4).18  Complexes [EBiFe3(CO)9] (E = Te, Se) displayed a BiEFe2 basal plane with an apical Fe(CO)3 fragment, in which both the Bi and chalcogen atom possessed an outward stereoactive lone pair. These square pyramidal complexes can undergo methylation and metalation via competitive 6s/5s and 6s/4s lone pairs selectivity, to give a 4s-methylated compound {(Me)SeFe3(CO)9}Bi, 6s-Cr(CO)5-decorated complexes [BiEFe3(CO)9{Cr(CO)5}] (E = Te, Se) (Scheme 1.4). The novel nucleophilicity of the 6s lone pair of the naked Bi atom can be well explained by XPS, XANES, and DFT calculations. These square pyramidal complexes also can be demetalated to give tetrahedral anionic complexes [{EFe2(CO)6}Bi] (E = Te, Se), in which the reactive sites can be understood by their corresponding HOMO orbitals.18  Importantly, these square pyramidal, tetrahedral, and Cr(CO)5-decorated complexes were found to have intra- and intermolecular Bi⋯E interactions to give ⋯Bi⋯E⋯ chains or Bi⋯E⋯E⋯Bi (E = Te or Se) dimers. These chains or dimeric units were further connected to their counterions through C–H⋯O(carbonyl) hydrogen bonds to give 2D supramolecular networks (Figure 1.6).

Scheme 1.4

Syntheses and reactivities of mixed Bi–chalcogen iron carbonyl complexes.

Scheme 1.4

Syntheses and reactivities of mixed Bi–chalcogen iron carbonyl complexes.

Close modal
Figure 1.6

A portion of (a) [Et4N][TeBiFe3(CO)9] (ref. code COFFEL) and (b) [Et4N][BiTeFe3(CO)9{Cr(CO)5}] (COFFOV).

Figure 1.6

A portion of (a) [Et4N][TeBiFe3(CO)9] (ref. code COFFEL) and (b) [Et4N][BiTeFe3(CO)9{Cr(CO)5}] (COFFOV).

Close modal

Similarly but differently, when reactions of A (A = ATe, ASe, AS) with SbCl3 were carried out under similar conditions, three novel pendant cluster-coordinated square pyramidal-based anionic complexes [{SbTeFe3(CO)9}{Te2Fe3(CO)9}], [{SbSeFe3(CO)9}{Se2Fe2(CO)6}], and [{SbSFe3(CO)9}{SFe3(CO)9}], were successfully obtained.19  These complexes each contained the ESbFe3(CO)9 (E = Te, Se, S) square pyramidal core that was further coordinated to the respective pendant fragment, Te2Fe3(CO)9, Se2Fe2(CO)6, or SFe3(CO)9, via the Sb atom. They showed high electrophilicity toward metal carbonylates, producing a series of transmetalated products. These metalated products included “spiked” square pyramidal anionic complexes [{SbEFe3(CO)9}{M(CO)x}] (M(CO)x = Fe(CO)4, E = Te, Se, S; Cr(CO)5, E = Se, S), and Mn(CO)4-bridged di-square pyramidal clusters [{SbEFe3(CO)9}2Mn(CO)4] (E = Se, S). Significantly, these ternary and quaternary complexes revealed O⋯O(carbonyl) or C–H⋯O(carbonyl) interactions to construct 2D and 3D supramolecular frameworks in the solid state (Figure 1.7). These rarely seen mixed pnictogens (Bi, Sb) and chalcogen (Te, Se, S) iron carbonyl clusters possessed important intra- and inter-molecular interactions in the solid state, facilitating efficient electron transports to result in tunable low energy gaps. The details will be discussed in Section 1.5.1.

Figure 1.7

A portion of (a) [Et4N][{SbSeFe3(CO)9}{Se2Fe2(CO)6}] (ELEZAZ) and (b) [Et4N][{SbSFe3(CO)9}2Mn(CO)4] (ELIBUZ).

Figure 1.7

A portion of (a) [Et4N][{SbSeFe3(CO)9}{Se2Fe2(CO)6}] (ELEZAZ) and (b) [Et4N][{SbSFe3(CO)9}2Mn(CO)4] (ELIBUZ).

Close modal

The first ternary Te–Ru–Cu cluster-based polymeric chain, {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]·THF}n, was synthesized from the reaction of K2TeO3 and Ru3(CO)12 with PPh4Br in MeOH followed by the addition of CuCl in MeCN. Alternatively, this polymer could also be synthesized upon the treatment of the CuX-bridged octahedral complexes [PPh4]2[Te2Ru4(CO)10(CuX)2] (X = Br, Cl) with the linking agent CuX (X = Cl, Br), respectively.20  X-ray analysis showed that polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]·THF}n contained the octahedral Te2Ru4(CO)10 units which were connected by two Cu2BrCl fragments, in which the opposite Ru–Ru edges each were bridged by the Cu2Br moiety of the bridging Cu2BrCl, to give a 1D infinite chain. The bridging chloride ions could further connect with the phenyl H atoms from the PPh4+ cations via weak hydrogen bonds to form a supramolecular network (Figure 1.8), which enhanced the stability in the solid state. This chain polymer showed surprising semiconducting behaviours with a small optical energy gap of about 0.37 eV. The related discussion will be shown in Section 1.5.1.

Figure 1.8

A portion of Te–Ru–Cu polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]·THF}n (GIHSEW).

Figure 1.8

A portion of Te–Ru–Cu polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]·THF}n (GIHSEW).

Close modal

On the basis of the versatile structural features and unique properties, metal carbonyl chalcogenide polymers are believed to have some potential applications. This section will describe some representative polymers regarding semiconducting behaviours, photodegradation, magnetism, catalysis, and adsorption/desorption properties.

The discovery of new semiconductors is one of the advanced targets of material science for chemists to pursue. Although quite a few conductive polymers have been reported,1d,1e  the conductive/semi-conductive metal carbonyl chalcogen-containing polymers or supramolecules were much less investigated. In 2007, the first Te–Ru–Cu polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]·THF}n was synthesized and found to exhibit semiconducting behaviours with the dc conductivity of (1–5)  ×  10−2−1 cm−1 and a small optical band gap of ca. 0.37 eV.20  The electron transport was determined by the electron density propagation along the chain units as supported by DFT calculations. Notably, its energy gap was found to be smaller than that of Te2Ru (0.491 eV),21  indicating that the incorporation of Cu would efficiently enhance the conductivity.

In 2008, the first ATe-based Te–Fe–Cu polymers, the mono-Cu-bridged polymer [Et4N]n[{ATe}Cu]n and the single- and double-dpy-linked polymer [{ATe}Cu2(dpy)1.5]n, were rationally synthesized.12  They were shown to exhibit semiconducting behaviours with low energy gaps (0.59 and 0.41 eV) and high dc conductivities (2  ×  10−2 and 5  ×  10−2−1 cm−1).12  The more efficient electron transport of the single- and double-dpy-linked polymer [{ATe}Cu2(dpy)1.5]n was proven via DFT calculations to be aided by the π⋯π interactions between the double dpy linkers. Later in 2017, a series of dipyridyl-linked ATe-based Te–Fe–Cu polymers, [{ATe}Cu2L]n, [{ATe}Cu2L2.5]n (L = bpea, bpee), and [{Cu2(bpp)4}({ATeCu}2bpp)]n were also reported to possess semiconducting behaviours with tunable optical energy gaps (1.43–1.52 eV) and dc conductivities (2.5  ×  10−3–2.2  ×  10−2−1 cm−1).13  The efficient electron transport of these dipyridyl-linked Te–Fe–Cu polymers was supported by the change of the oxidation state of the Cu atoms using XPS and XANES. These results confirmed the electron propagation from electron-rich metal clusters ATe to the Cu centres, then to the dipyridyl linkers and polymeric frameworks.13  It was surprising to find that the most conjugated bpp-linked polymer possessed the lowest optical energy gap (1.43 eV) and pronounced dc conductivity (1.5  ×  10−2−1 cm−1) (Figure 1.9). These results can be attributed to the significant C–H⋯O(carbonyl) and C–H⋯π(bpp) interactions within the framework. These results strongly demonstrated that COs played an essential role in facilitating the electron communication of metal carbonyl-based polymeric frameworks.

Figure 1.9

(a) Room-temperature optical reflectance spectrum and (b) frequency-dependent optical conductivity of polymer [{Cu2(bpp)4}({ATeCu}2bpp)]n.

Figure 1.9

(a) Room-temperature optical reflectance spectrum and (b) frequency-dependent optical conductivity of polymer [{Cu2(bpp)4}({ATeCu}2bpp)]n.

Close modal

The dppe-bridged AS-based S–Fe–Cu polymer, [(μ4-AS)Cu2(MeCN)2(dppe)]n, was found to be synthesized from its discrete precursor, [(μ3-AS)Cu2(dppe)], via vapochemical polymerization. This polymer could undergo unique mechanochemical depolymerization back to its discrete complex.15  Surprisingly, the S–Fe–Cu–dppe polymer possessed a lower energy gap (1.69 eV) than the discrete complex (1.71 eV). The subtle difference was attributed to the bridging dppe unit, although dppe is usually considered as a poor electron-transfer ligand.

Recently, a series of inorganic–organic hybrid ASe-based Cu polymers with variable cluster bonding modes were mechanochemically synthesized as described in Section 1.4.2.16  These Se–Fe–Cu polymers were found to possess low energy gaps of 1.49–1.72 eV that increased based on their structure modes following the order: cluster-linked, cluster-blocked, and cluster-pendant coordination fashion. Notably, the most conjugation-interrupted bpp-linked polymer [(μ4-ASe)Cu2(bpp)2]n had a relatively lower energy gap (1.58 eV), mainly ascribed to numerous C–H(bpp)⋯O(carbonyl) hydrogen bonds and C–H⋯π(bpp) interactions within the polymeric framework with the aid of X-ray analysis, the density of state (DOS) and band structure calculations. The electrical conductivity of three representative polymers, [(μ4-ASe)Cu2(bpp)2]n, [(μ3-ASe)Cu2(bpea)]n, and [(μ3-ASe)Cu2(dpy)3]n, were measured to be 3.13  ×  10−7 (Figure 1.10), 2.92 × 10−7, and 2.30  ×  10−7 S cm−1, respectively. These electrical conductivities were parallel to the trend of their energy gaps, showing semiconducting behaviours.

Figure 1.10

The electrical conductivity of the pressed pellet sample of polymer [(μ4-ASe)Cu2(bpp)2]n.

Figure 1.10

The electrical conductivity of the pressed pellet sample of polymer [(μ4-ASe)Cu2(bpp)2]n.

Close modal

Apart from the semiconducting chalcogen–metal carbonyl polymers mentioned above, some discrete clusters with supramolecular networks were also found to have low energy gaps. In the Te–Mn system, a series of small- to large-sized polynuclear Te–Mn complexes have been synthesized and structurally characterized, as mentioned in Section 1.3.1. These manganese complexes possessed a wide range of energy gaps (1.06–1.62 eV).8  Besides, the rare class of pnictogen (Bi, Sb) and chalcogen (Te, Se, S)-containing iron carbonyl clusters also possessed low-energy-gap characteristics of 1.01–1.21 eV in the Bi series and 0.84–1.48 eV for the Sb series.18,19  Although structurally characterized as discrete molecular systems, these complexes can be extended into supramolecular frameworks via weak but significant C–H(counterion)⋯O(carbonyl) and O⋯O(carbonyl) interactions, as evidenced by X-ray analysis and DFT calculations. The formation of supramolecular frameworks is responsible for their unexpected low energy gaps.

Recently, water/light-stable Se–Fe–Cu semiconducting polymers, [(μ4-ASe)Cu2(bpp)2]n, [(μ3-ASe)Cu2(bpea)2.5]n, and [(μ3-ASe)Cu2(dpy)3]n, were shown to have photodegradation activities toward para-nitrophenol (PNP) under the Xe irradiation in water (Figure 1.11a).16  Their degradation rate obeyed the pseudo-first-order kinetics with kobs being 6.46  ×  10−3 ([(μ4-ASe)Cu2(bpp)2]n), 6.08 × 10−3 ([(μ3-ASe)Cu2(bpea)2.5]n), and 1.21  ×  10−3 min−1 ([(μ3-ASe)Cu2(dpy)3]n) (Figure 1.11b). The results indicated that cluster-linked [(μ4-ASe)Cu2(bpp)2]n possessed a higher degradation efficiency in comparison with cluster-pendant polymers [(μ3-ASe)Cu2(bpea)2.5]n and [(μ3-ASe)Cu2(dpy)3]n, in agreement with their increased energy gaps (discussed above in the section of semiconducting properties). Furthermore, the photodegradation of 2,4-dinitrophenol (2,4-DNP) and organic dyes (methylene blue (MB) and sunset yellow (SY)) by the most efficient polymer [(μ4-ASe)Cu2(bpp)2]n was also successfully achieved with good pseudo-first-order kinetics.16  These polymers were shown to serve as efficient agents for the photodegradation of nitroaromatics and organic dyes, implying their potential uses as catalysts for recycling dye wastewater.

Figure 1.11

(a) The absorption spectra of the photodegradation of PNP by polymer [(μ4-ASe)Cu2(bpp)2]n and (b) kinetic data for the photodegradation of PNP by polymers [(μ4-ASe)Cu2(bpp)2]n (green), [(μ3-ASe)Cu2(bpea)2.5]n (black), and [(μ3-ASe)Cu2(dpy)3]n (blue).

Figure 1.11

(a) The absorption spectra of the photodegradation of PNP by polymer [(μ4-ASe)Cu2(bpp)2]n and (b) kinetic data for the photodegradation of PNP by polymers [(μ4-ASe)Cu2(bpp)2]n (green), [(μ3-ASe)Cu2(bpea)2.5]n (black), and [(μ3-ASe)Cu2(dpy)3]n (blue).

Close modal

Significantly few metal carbonyl chalcogenide polymers showed magnetic properties due to the strong-field CO ligands. Two electron-precise Te–Mn anionic clusters [Mn6Te6(CO)18]4− and [Mn6Te10(CO)18]4− were shown to exhibit unexpected paramagnetic properties with μeff = 2.60 and 2.45 μB at 300 K (Figure 1.12a).8  These hexamanganese complexes represent the first examples of electron-precise paramagnetic manganese telluride carbonyl complexes. XPS and EPR analyses of these Te–Mn complexes further established the oxidation states of the Mn atoms, exchange couplings among the magnetic centres, hyperfine splittings of 55Mn (I = 5/2), and zero-field splitting parameters for the triplet state (Figure 1.12b).8 

Figure 1.12

(a) Temperature-dependent magnetic susceptibility data for [Et4N]4[Mn6Te6(CO)18] and (b) experimental (blue line) and simulated (red line) 100 K EPR spectra of a frozen MeCN solution of [Et4N]4[Mn6Te6(CO)18].

Figure 1.12

(a) Temperature-dependent magnetic susceptibility data for [Et4N]4[Mn6Te6(CO)18] and (b) experimental (blue line) and simulated (red line) 100 K EPR spectra of a frozen MeCN solution of [Et4N]4[Mn6Te6(CO)18].

Close modal

Due to the electron-rich nature and high stability, chalcogen-containing metal carbonyl polymers and supramolecules were believed to have potential applications in catalysis. In 2019, a novel family of NHC-functionalized ternary Se–Fe–Cu compounds, [ASe{Cu(NHC)}2] (NHC = Me2-imy, Me2-bimy, iPr2-bimy, Me2-Cl2-imy), were obtained and structurally characterized.17  These NHC compounds could serve as catalysts in the Suzuki homocoupling coupling reaction of arylboronic acids with high turnovers (80–87) under mild conditions. Importantly, these Se-containing NHC compounds further represented excellent models for studying chalcogen effects compared to their Te-analogues,22  which was demonstrated by their catalytic performances and electrochemical behaviours, supported by DFT calculations.

Host–guest chemistry was an important topic for the coordination polymer due to various secondary interactions between organic/inorganic guest molecules and host polymers that could modulate their physical and chemical properties. Some reports of metal carbonyl chalcogenide polymers regarding adsorption/desorption properties have been reported. In 2006, the rectangular S–Re carbonyl compound [{(SC4H9)2Re2(CO)6}2(dpy)2] was found to be capable of encapsulating the pyrene molecule or AgNO3.9  These reactions would lead to formations of the pyrene-introduced polymer [{(SC4H9)2Re2(CO)6}2(dpy)2(pyrene)]n and the Ag-intercalated polymer [{(SC4H9)2Re2(CO)6}2(dpy)2(AgNO3)2(C3H6O)2}·C3H6O]n. The interaction of the pyrene- and AgNO3-intercalated products in solutions was studied by 1H NMR, UV–vis, and fluorescence spectroscopies. The π–π, CH⋯π, and S⋯Ag⋯O interactions of these intercalated products were further found in the solid state, which could help stabilize their resulting frameworks. In 2010, the S2Fe2 cluster-incorporated, β-cyclodextrin-hosted polymer Na{(SCH2N(C6H4SO3)CH2S)}[Fe(CO)3]2·2β-CyD has been synthesized and reported.10b  The included S2Fe2 cluster [(SCH2N(C6H4SO3)CH2S)Fe(CO)3] had good intermolecular interactions with β-CyD, as evidenced by NMR spectra. The inclusion polymer further exhibited the negative-shifted electrochemical peaks for the catalytic H2 production compared to the free cluster, reflecting the hydrophobic characteristics of the β-CyD. This result provided a new host–guest approach to a biomimetic cavity with a hydrogenase active site.

This chapter is intended to give an overview of the recent progress of carbonyl chalcogenide cluster-based coordination polymers. They can be obtained via various synthetic methods, such as solution-based, hydro(solvo)thermal, mechanochemical, UV irradiated, and vapochemical reactions. These polymers were constructed mainly by metal–chalcogen linkages, while some supramolecular frameworks could be formed by intra- or intermolecular C–H⋯O(carbonyl) hydrogen bonds, which can also enhance their stabilities in the solid state. Due to the electron-rich nature and abundant redox properties of the incorporated metal carbonyl cluster units, their resulting polymers were demonstrated to have a wide range of applications, i.e. semiconductors, photodegradation activities, magnetism, catalysis, and guest molecule absorption/desorption. Although this research area has received growing interest, the structural characterizations of these polymers still relied on the conventional X-ray analysis of single crystals that were difficult to obtain mainly due to their poor solubility in most organic solvents. In the future, the study of metal carbonyl cluster-based chalcogenide polymers should focus on discovering systematic synthetic routes and their special properties/applications as well as rationalizing their intriguing structure–property relationships.

Minghuey Shieh wishes to thank the Ministry of Science and Technology of Taiwan (MOST 110-2113-M-003-014) for the continuous support of her research. She also thanks all graduate students in her research group for their efforts on this topic. She is also grateful to the National Center for High-Performance Computing and National Synchrotron Radiation Research Center of Taiwan for the technical support.

1a.
Furukawa
 
H.
Cordova
 
K. E.
O'Keeffe
 
M.
Yaghi
 
O. M.
Science
2013
, vol. 
341
 pg. 
1230444
 
1b.
Thanasekaran
 
P.
Su
 
C.-H.
Liu
 
Y.-H.
Lu
 
K.-L.
Coord. Chem. Rev.
2021
, vol. 
442
 pg. 
213987
 
1c.
Sun
 
J.-K.
Yang
 
X.-D.
Yang
 
G.-Y.
Zhang
 
J.
Coord. Chem. Rev.
2019
, vol. 
378
 pg. 
533
 
1d.
Xie
 
L. S.
Skorupskii
 
G.
Dincă
 
M.
Chem. Rev.
2020
, vol. 
120
 pg. 
8536
 
1e.
Thorarinsdottir
 
A. E.
Harris
 
T. D.
Chem. Rev.
2020
, vol. 
120
 pg. 
8716
 
2a.
Xie
 
J.
Wang
 
L.
Anderson
 
J. S.
Chem. Sci.
2020
, vol. 
11
 (pg. 
8350
-
8372
)
2b.
Yue
 
Q.
Gao
 
E.-Q.
Coord. Chem. Rev.
2019
, vol. 
382
 pg. 
1
 
3a.
Shieh
 
M.
Liu
 
Y.-H.
Li
 
Y.-H.
Lin
 
R. Y.
CrystEngComm
2019
, vol. 
21
 pg. 
7341
 
3b.
Whitmire
 
K. H.
Coord. Chem. Rev.
2018
, vol. 
376
 pg. 
114
 
3c.
Peresypkina
 
E.
Virovets
 
A.
Scheer
 
M.
Coord. Chem. Rev.
2021
, vol. 
446
 pg. 
213995
 
3d.
Shieh
 
M.
Miu
 
C.-Y.
Chu
 
Y.-Y.
Lin
 
C.-N.
Coord. Chem. Rev.
2012
, vol. 
256
 pg. 
637
 
3e.
Shieh
 
M.
Yu
 
C.-C.
J. Organomet. Chem.
2017
, vol. 
849–850
 pg. 
219
 
4a.
Cooper
 
M. K.
Duckworth
 
P. A.
Henrick
 
K.
McPartlin
 
M.
J. Organomet. Chem.
1981
, vol. 
212
 (pg. 
C10
-
C12
)
4b.
Cooper
 
M. K.
Duckworth
 
P. A.
Henrick
 
K.
McPartlin
 
M.
J. Chem. Soc., Dalton Trans.
1981
pg. 
2357
 
5.
Crispini
 
A.
Errington
 
R. J.
Fisher
 
G. A.
Funke
 
F. J.
Norman
 
N. C.
Orpen
 
A. G.
Stratford
 
S. E.
Struve
 
O.
J. Chem. Soc., Dalton Trans.
1994
pg. 
1327
 
6.
Almaraz
 
E.
Foley
 
W. S.
Denny
 
J. A.
Reibenspies
 
J. H.
Golden
 
M. L.
Darensbourg
 
M. Y.
Inorg. Chem.
2009
, vol. 
48
 pg. 
5288
 
7.
Preda
 
A. M.
Raţ
 
C. I.
Silvestru
 
C.
Breunig
 
H. J.
Lang
 
H.
Rüffer
 
T.
Mehring
 
M.
Dalton Trans.
2013
, vol. 
42
 pg. 
1144
 
8.
Shieh
 
M.
Liu
 
Y.-H.
Lin
 
T.-S.
Lin
 
Y.-C.
Cheng
 
W.-K.
Lin
 
R. Y.
Inorg. Chem.
2020
, vol. 
59
 pg. 
6923
 
9.
Manimaran
 
B.
Lai
 
L.-J.
Thanasekaran
 
P.
Wu
 
J.-Y.
Liao
 
R.-T.
Tseng
 
T.-W.
Liu
 
Y.-H.
Lee
 
G.-H.
Peng
 
S.-M.
Lu
 
K.-L.
Inorg. Chem.
2006
, vol. 
45
 pg. 
8070
 
10a.
Singleton
 
M. L.
Crouthers
 
D. J.
Duttweiler, III
 
R. P.
Reibenspies
 
J. H.
Darensbourg
 
M. Y.
Inorg. Chem.
2011
, vol. 
50
 pg. 
5015
 
10b.
Singleton
 
M. L.
Reibenspies
 
J. H.
Darensbourg
 
M. Y.
J. Am. Chem. Soc.
2010
, vol. 
132
 pg. 
8870
 
11.
Liaw
 
W.-F.
Tsai
 
W.-T.
Gau
 
H.-B.
Lee
 
C.-M.
Chou
 
S.-Y.
Chen
 
W.-Y.
Lee
 
G.-H.
Inorg. Chem.
2003
, vol. 
42
 pg. 
2783
 
12.
Shieh
 
M.
Ho
 
C.-H.
Sheu
 
W.-S.
Chen
 
B.-G.
Chu
 
Y.-Y.
Miu
 
C.-Y.
Liu
 
H.-L.
Shen
 
C.-C.
J. Am. Chem. Soc.
2008
, vol. 
130
 pg. 
14114
 
13.
Shieh
 
M.
Yu
 
C.-C.
Miu
 
C.-Y.
Kung
 
C.-H.
Huang
 
C.-Y.
Liu
 
Y.-H.
Liu
 
H.-L.
Shen
 
C.-C.
Chem. – Eur. J.
2017
, vol. 
23
 pg. 
11261
 
14a.
Friščić
 
T.
Mottillo
 
C.
Titi
 
H. M.
Angew. Chem., Int. Ed.
2020
, vol. 
59
 pg. 
1018
 
14b.
Kole
 
G. K.
Vittal
 
J. J.
Chem. Soc. Rev.
2013
, vol. 
42
 pg. 
1755
 
15.
Lin
 
C.-N.
Jhu
 
W.-T.
Shieh
 
M.
Chem. Commun.
2014
, vol. 
50
 pg. 
1134
 
16.
Liu
 
Y.-H.
Huang
 
K.-T.
Chen
 
W.-C.
Li
 
Y.-W.
Ke
 
W.-M.
Ho
 
B.-R.
Hsu
 
M.-C.
Li
 
Y.-H.
Shieh
 
M.
Inorg. Chem.
2021
, vol. 
60
 pg. 
18270
 
17.
Shieh
 
M.
Liu
 
Y.-H.
Wang
 
C.-C.
Jian
 
S.-H.
Lin
 
C.-N.
Chen
 
Y.-M.
Huang
 
C.-Y.
New J. Chem.
2019
, vol. 
43
 pg. 
11832
 
18.
Shieh
 
M.
Liu
 
Y.-H.
Huang
 
C.-Y.
Chen
 
S.-W.
Cheng
 
W.-K.
Chien
 
L.-T.
Inorg. Chem.
2019
, vol. 
58
 pg. 
6706
 
19.
Yeh
 
H.-H.
Hsu
 
M.-C.
Li
 
Y.-H.
Hsu
 
Y.-N.
Shr
 
F.-Y.
Shieh
 
M.
J. Organomet. Chem.
2021
, vol. 
937
 pg. 
121717
 
20.
Shieh
 
M.
Hsu
 
M.-H.
Sheu
 
W.-S.
Jang
 
L.-F.
Lin
 
S.-F.
Chu
 
Y.-Y.
Miu
 
C.-Y.
Lai
 
Y.-W.
Liu
 
H.-L.
Her
 
J.-L.
Chem. – Eur. J.
2007
, vol. 
13
 pg. 
6605
 
21.
Liao
 
P. C.
Huang
 
J. K.
Huang
 
Y. S.
Yang
 
T. R.
Solid State Commun.
1996
, vol. 
98
 pg. 
279
 
22.
Lin
 
C.-N.
Huang
 
C.-Y.
Yu
 
C.-C.
Chen
 
Y.-M.
Ke
 
W.-M.
Wang
 
G.-J.
Lee
 
G.-A.
Shieh
 
M.
Dalton Trans.
2015
, vol. 
44
 pg. 
16675
 

Figures & Tables

Figure 1.1

A portion of (a) [Na(18-crown-6)][W(CO)5(SH)] (ref. code NACRWA), (b) [Na(18-crown-6)][W2(CO)10(SH)] (NACRWB), (c) [Bi(SCN){Mo(CO)3(Cp)}2]n (WETRAO), (d) [Zn(tbtp-dach)W(CO)5]n (RULXIG), and (e) cyclo-[{2-(2′,6′-iPr2C6H3NCH)C6H4}SbS]2[W(CO)5] (EPOCIX). Bright-blue, bright-green, yellow, pink, and orange dashed lines represent Bi⋯N, Zn⋯O, O⋯H, C–H⋯π, and S⋯H interactions, respectively.

Figure 1.1

A portion of (a) [Na(18-crown-6)][W(CO)5(SH)] (ref. code NACRWA), (b) [Na(18-crown-6)][W2(CO)10(SH)] (NACRWB), (c) [Bi(SCN){Mo(CO)3(Cp)}2]n (WETRAO), (d) [Zn(tbtp-dach)W(CO)5]n (RULXIG), and (e) cyclo-[{2-(2′,6′-iPr2C6H3NCH)C6H4}SbS]2[W(CO)5] (EPOCIX). Bright-blue, bright-green, yellow, pink, and orange dashed lines represent Bi⋯N, Zn⋯O, O⋯H, C–H⋯π, and S⋯H interactions, respectively.

Close modal
Scheme 1.1

Synthesis and structural transformations of a series of Mn telluride complexes.

Scheme 1.1

Synthesis and structural transformations of a series of Mn telluride complexes.

Close modal
Figure 1.2

A portion of (a) an 1D chain in crystal [TMBA]2[Mn4Te(CO)16] (ref. code VUGKOA), (b) a 2D plane in crystal [TMBA]2[Mn2Te2(CO)8] (VUGKUG), (c) an 1D chain in crystal [Et4N]2[HMn3Te2(CO)9] (VUGLAN), (d) a 2D plane in crystal [Et4N]4[Mn6Te6(CO)18]·2MeCN (VUGLER), (e) a 2D plane in crystal [Et4N]4[Mn6Te10(CO)18] (VUGLIV), and (f) a 2D plane in crystal [PPN]2[{HMn3Te2(CO)10}2] (VUGLOB). Light-green dashed line represents the O⋯H interaction.

Figure 1.2

A portion of (a) an 1D chain in crystal [TMBA]2[Mn4Te(CO)16] (ref. code VUGKOA), (b) a 2D plane in crystal [TMBA]2[Mn2Te2(CO)8] (VUGKUG), (c) an 1D chain in crystal [Et4N]2[HMn3Te2(CO)9] (VUGLAN), (d) a 2D plane in crystal [Et4N]4[Mn6Te6(CO)18]·2MeCN (VUGLER), (e) a 2D plane in crystal [Et4N]4[Mn6Te10(CO)18] (VUGLIV), and (f) a 2D plane in crystal [PPN]2[{HMn3Te2(CO)10}2] (VUGLOB). Light-green dashed line represents the O⋯H interaction.

Close modal
Figure 1.3

A portion of (a) [{(CO)3Re(SC4H9)2Re(CO)3}2(dpy)2(pyrene)]n (ref. code HEPLOE) and (b) [{(CO)3Re(SC4H9)2Re(CO)3}2(dpy)2(AgNO3)2(C3H6O)2}·C3H6O]n (HEPLUK). Light-green dashed line represents the O⋯H interaction.

Figure 1.3

A portion of (a) [{(CO)3Re(SC4H9)2Re(CO)3}2(dpy)2(pyrene)]n (ref. code HEPLOE) and (b) [{(CO)3Re(SC4H9)2Re(CO)3}2(dpy)2(AgNO3)2(C3H6O)2}·C3H6O]n (HEPLUK). Light-green dashed line represents the O⋯H interaction.

Close modal
Scheme 1.2

Synthesis of the Te–Fe–Cu cluster-based polymers.

Scheme 1.2

Synthesis of the Te–Fe–Cu cluster-based polymers.

Close modal
Figure 1.4

A portion of (a) [{ATe}Cu]n (ref. code XOMSEY), (b) [{ATe}Cu2(dpy)1.5]n (XOMSIC), (c) [{ATe}Cu2bpee]n (WAYQOF), (d) [{ATe}Cu2L2.5]n (L = bpee, WAYRAS), (e) [{Cu2(bpp)4}({ATeCu}2bpp)]n (WAYRIA), and (f) [(AS)Cu2(dppe)(MeCN)2]n (PINTAJ). The H atoms in (e) were omitted for clarity.

Figure 1.4

A portion of (a) [{ATe}Cu]n (ref. code XOMSEY), (b) [{ATe}Cu2(dpy)1.5]n (XOMSIC), (c) [{ATe}Cu2bpee]n (WAYQOF), (d) [{ATe}Cu2L2.5]n (L = bpee, WAYRAS), (e) [{Cu2(bpp)4}({ATeCu}2bpp)]n (WAYRIA), and (f) [(AS)Cu2(dppe)(MeCN)2]n (PINTAJ). The H atoms in (e) were omitted for clarity.

Close modal
Scheme 1.3

Synthesis and the reversible structural transformation of the dppe-linked S–Fe–Cu-based cluster and polymer.

Scheme 1.3

Synthesis and the reversible structural transformation of the dppe-linked S–Fe–Cu-based cluster and polymer.

Close modal
Figure 1.5

A portion of (a) [(μ4-ASe)Cu2(bpp)2]n (ref. code SALJAU), (b) [(μ4-ASe)Cu2(MeCN)(dpy)1.5]n (SALHUM), and (c) [(μ3-ASe)Cu2(dpy)3]n (SALJEY). The H atoms and COs in (a) and (b) were omitted for clarity.

Figure 1.5

A portion of (a) [(μ4-ASe)Cu2(bpp)2]n (ref. code SALJAU), (b) [(μ4-ASe)Cu2(MeCN)(dpy)1.5]n (SALHUM), and (c) [(μ3-ASe)Cu2(dpy)3]n (SALJEY). The H atoms and COs in (a) and (b) were omitted for clarity.

Close modal
Scheme 1.4

Syntheses and reactivities of mixed Bi–chalcogen iron carbonyl complexes.

Scheme 1.4

Syntheses and reactivities of mixed Bi–chalcogen iron carbonyl complexes.

Close modal
Figure 1.6

A portion of (a) [Et4N][TeBiFe3(CO)9] (ref. code COFFEL) and (b) [Et4N][BiTeFe3(CO)9{Cr(CO)5}] (COFFOV).

Figure 1.6

A portion of (a) [Et4N][TeBiFe3(CO)9] (ref. code COFFEL) and (b) [Et4N][BiTeFe3(CO)9{Cr(CO)5}] (COFFOV).

Close modal
Figure 1.7

A portion of (a) [Et4N][{SbSeFe3(CO)9}{Se2Fe2(CO)6}] (ELEZAZ) and (b) [Et4N][{SbSFe3(CO)9}2Mn(CO)4] (ELIBUZ).

Figure 1.7

A portion of (a) [Et4N][{SbSeFe3(CO)9}{Se2Fe2(CO)6}] (ELEZAZ) and (b) [Et4N][{SbSFe3(CO)9}2Mn(CO)4] (ELIBUZ).

Close modal
Figure 1.8

A portion of Te–Ru–Cu polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]·THF}n (GIHSEW).

Figure 1.8

A portion of Te–Ru–Cu polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2]·THF}n (GIHSEW).

Close modal
Figure 1.9

(a) Room-temperature optical reflectance spectrum and (b) frequency-dependent optical conductivity of polymer [{Cu2(bpp)4}({ATeCu}2bpp)]n.

Figure 1.9

(a) Room-temperature optical reflectance spectrum and (b) frequency-dependent optical conductivity of polymer [{Cu2(bpp)4}({ATeCu}2bpp)]n.

Close modal
Figure 1.10

The electrical conductivity of the pressed pellet sample of polymer [(μ4-ASe)Cu2(bpp)2]n.

Figure 1.10

The electrical conductivity of the pressed pellet sample of polymer [(μ4-ASe)Cu2(bpp)2]n.

Close modal
Figure 1.11

(a) The absorption spectra of the photodegradation of PNP by polymer [(μ4-ASe)Cu2(bpp)2]n and (b) kinetic data for the photodegradation of PNP by polymers [(μ4-ASe)Cu2(bpp)2]n (green), [(μ3-ASe)Cu2(bpea)2.5]n (black), and [(μ3-ASe)Cu2(dpy)3]n (blue).

Figure 1.11

(a) The absorption spectra of the photodegradation of PNP by polymer [(μ4-ASe)Cu2(bpp)2]n and (b) kinetic data for the photodegradation of PNP by polymers [(μ4-ASe)Cu2(bpp)2]n (green), [(μ3-ASe)Cu2(bpea)2.5]n (black), and [(μ3-ASe)Cu2(dpy)3]n (blue).

Close modal
Figure 1.12

(a) Temperature-dependent magnetic susceptibility data for [Et4N]4[Mn6Te6(CO)18] and (b) experimental (blue line) and simulated (red line) 100 K EPR spectra of a frozen MeCN solution of [Et4N]4[Mn6Te6(CO)18].

Figure 1.12

(a) Temperature-dependent magnetic susceptibility data for [Et4N]4[Mn6Te6(CO)18] and (b) experimental (blue line) and simulated (red line) 100 K EPR spectra of a frozen MeCN solution of [Et4N]4[Mn6Te6(CO)18].

Close modal

Contents

References

1a.
Furukawa
 
H.
Cordova
 
K. E.
O'Keeffe
 
M.
Yaghi
 
O. M.
Science
2013
, vol. 
341
 pg. 
1230444
 
1b.
Thanasekaran
 
P.
Su
 
C.-H.
Liu
 
Y.-H.
Lu
 
K.-L.
Coord. Chem. Rev.
2021
, vol. 
442
 pg. 
213987
 
1c.
Sun
 
J.-K.
Yang
 
X.-D.
Yang
 
G.-Y.
Zhang
 
J.
Coord. Chem. Rev.
2019
, vol. 
378
 pg. 
533
 
1d.
Xie
 
L. S.
Skorupskii
 
G.
Dincă
 
M.
Chem. Rev.
2020
, vol. 
120
 pg. 
8536
 
1e.
Thorarinsdottir
 
A. E.
Harris
 
T. D.
Chem. Rev.
2020
, vol. 
120
 pg. 
8716
 
2a.
Xie
 
J.
Wang
 
L.
Anderson
 
J. S.
Chem. Sci.
2020
, vol. 
11
 (pg. 
8350
-
8372
)
2b.
Yue
 
Q.
Gao
 
E.-Q.
Coord. Chem. Rev.
2019
, vol. 
382
 pg. 
1
 
3a.
Shieh
 
M.
Liu
 
Y.-H.
Li
 
Y.-H.
Lin
 
R. Y.
CrystEngComm
2019
, vol. 
21
 pg. 
7341
 
3b.
Whitmire
 
K. H.
Coord. Chem. Rev.
2018
, vol. 
376
 pg. 
114
 
3c.
Peresypkina
 
E.
Virovets
 
A.
Scheer
 
M.
Coord. Chem. Rev.
2021
, vol. 
446
 pg. 
213995
 
3d.
Shieh
 
M.
Miu
 
C.-Y.
Chu
 
Y.-Y.
Lin
 
C.-N.
Coord. Chem. Rev.
2012
, vol. 
256
 pg. 
637
 
3e.
Shieh
 
M.
Yu
 
C.-C.
J. Organomet. Chem.
2017
, vol. 
849–850
 pg. 
219
 
4a.
Cooper
 
M. K.
Duckworth
 
P. A.
Henrick
 
K.
McPartlin
 
M.
J. Organomet. Chem.
1981
, vol. 
212
 (pg. 
C10
-
C12
)
4b.
Cooper
 
M. K.
Duckworth
 
P. A.
Henrick
 
K.
McPartlin
 
M.
J. Chem. Soc., Dalton Trans.
1981
pg. 
2357
 
5.
Crispini
 
A.
Errington
 
R. J.
Fisher
 
G. A.
Funke
 
F. J.
Norman
 
N. C.
Orpen
 
A. G.
Stratford
 
S. E.
Struve
 
O.
J. Chem. Soc., Dalton Trans.
1994
pg. 
1327
 
6.
Almaraz
 
E.
Foley
 
W. S.
Denny
 
J. A.
Reibenspies
 
J. H.
Golden
 
M. L.
Darensbourg
 
M. Y.
Inorg. Chem.
2009
, vol. 
48
 pg. 
5288
 
7.
Preda
 
A. M.
Raţ
 
C. I.
Silvestru
 
C.
Breunig
 
H. J.
Lang
 
H.
Rüffer
 
T.
Mehring
 
M.
Dalton Trans.
2013
, vol. 
42
 pg. 
1144
 
8.
Shieh
 
M.
Liu
 
Y.-H.
Lin
 
T.-S.
Lin
 
Y.-C.
Cheng
 
W.-K.
Lin
 
R. Y.
Inorg. Chem.
2020
, vol. 
59
 pg. 
6923
 
9.
Manimaran
 
B.
Lai
 
L.-J.
Thanasekaran
 
P.
Wu
 
J.-Y.
Liao
 
R.-T.
Tseng
 
T.-W.
Liu
 
Y.-H.
Lee
 
G.-H.
Peng
 
S.-M.
Lu
 
K.-L.
Inorg. Chem.
2006
, vol. 
45
 pg. 
8070
 
10a.
Singleton
 
M. L.
Crouthers
 
D. J.
Duttweiler, III
 
R. P.
Reibenspies
 
J. H.
Darensbourg
 
M. Y.
Inorg. Chem.
2011
, vol. 
50
 pg. 
5015
 
10b.
Singleton
 
M. L.
Reibenspies
 
J. H.
Darensbourg
 
M. Y.
J. Am. Chem. Soc.
2010
, vol. 
132
 pg. 
8870
 
11.
Liaw
 
W.-F.
Tsai
 
W.-T.
Gau
 
H.-B.
Lee
 
C.-M.
Chou
 
S.-Y.
Chen
 
W.-Y.
Lee
 
G.-H.
Inorg. Chem.
2003
, vol. 
42
 pg. 
2783
 
12.
Shieh
 
M.
Ho
 
C.-H.
Sheu
 
W.-S.
Chen
 
B.-G.
Chu
 
Y.-Y.
Miu
 
C.-Y.
Liu
 
H.-L.
Shen
 
C.-C.
J. Am. Chem. Soc.
2008
, vol. 
130
 pg. 
14114
 
13.
Shieh
 
M.
Yu
 
C.-C.
Miu
 
C.-Y.
Kung
 
C.-H.
Huang
 
C.-Y.
Liu
 
Y.-H.
Liu
 
H.-L.
Shen
 
C.-C.
Chem. – Eur. J.
2017
, vol. 
23
 pg. 
11261
 
14a.
Friščić
 
T.
Mottillo
 
C.
Titi
 
H. M.
Angew. Chem., Int. Ed.
2020
, vol. 
59
 pg. 
1018
 
14b.
Kole
 
G. K.
Vittal
 
J. J.
Chem. Soc. Rev.
2013
, vol. 
42
 pg. 
1755
 
15.
Lin
 
C.-N.
Jhu
 
W.-T.
Shieh
 
M.
Chem. Commun.
2014
, vol. 
50
 pg. 
1134
 
16.
Liu
 
Y.-H.
Huang
 
K.-T.
Chen
 
W.-C.
Li
 
Y.-W.
Ke
 
W.-M.
Ho
 
B.-R.
Hsu
 
M.-C.
Li
 
Y.-H.
Shieh
 
M.
Inorg. Chem.
2021
, vol. 
60
 pg. 
18270
 
17.
Shieh
 
M.
Liu
 
Y.-H.
Wang
 
C.-C.
Jian
 
S.-H.
Lin
 
C.-N.
Chen
 
Y.-M.
Huang
 
C.-Y.
New J. Chem.
2019
, vol. 
43
 pg. 
11832
 
18.
Shieh
 
M.
Liu
 
Y.-H.
Huang
 
C.-Y.
Chen
 
S.-W.
Cheng
 
W.-K.
Chien
 
L.-T.
Inorg. Chem.
2019
, vol. 
58
 pg. 
6706
 
19.
Yeh
 
H.-H.
Hsu
 
M.-C.
Li
 
Y.-H.
Hsu
 
Y.-N.
Shr
 
F.-Y.
Shieh
 
M.
J. Organomet. Chem.
2021
, vol. 
937
 pg. 
121717
 
20.
Shieh
 
M.
Hsu
 
M.-H.
Sheu
 
W.-S.
Jang
 
L.-F.
Lin
 
S.-F.
Chu
 
Y.-Y.
Miu
 
C.-Y.
Lai
 
Y.-W.
Liu
 
H.-L.
Her
 
J.-L.
Chem. – Eur. J.
2007
, vol. 
13
 pg. 
6605
 
21.
Liao
 
P. C.
Huang
 
J. K.
Huang
 
Y. S.
Yang
 
T. R.
Solid State Commun.
1996
, vol. 
98
 pg. 
279
 
22.
Lin
 
C.-N.
Huang
 
C.-Y.
Yu
 
C.-C.
Chen
 
Y.-M.
Ke
 
W.-M.
Wang
 
G.-J.
Lee
 
G.-A.
Shieh
 
M.
Dalton Trans.
2015
, vol. 
44
 pg. 
16675
 
Close Modal

or Create an Account

Close Modal
Close Modal