Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters: Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties

Yu Huei Li; I. Hsuan Fu; Yen Ming Chen; Hui Lung Chen; Minghuey Shieh

doi:10.1016/j.jorganchem.2026.124031

Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters: Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties

Yu Huei Li
, I. Hsuan Fu
, Yen Ming Chen
, Hui Lung Chen^*
, Minghuey Shieh

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Efficient synthetic routes to metal carbonyl cluster–based polymers via ion-exchange processes remain unexplored. In this study, a mechanochemical ion-exchange strategy was developed using a one-dimensional (1D) Cu–dpy (dpy = 4,4’-dipyridyl) template polymer, [Cu(dpy)(MeCN)₂(BF₄)]_n, and Hg-bridged iron carbonyl chalcogenide clusters, [Et₄N]₂[Hg{EFe₃(CO)₉}₂] (E = Te, Se, S), to construct novel polymeric materials. When polymer [Cu(dpy)(MeCN)₂(BF₄)]_n was treated with [Et₄N]₂[Hg{TeFe₃(CO)₉}₂] in a ratio of 2: 1 via liquid-assisted grinding (LAG), a 1D polymer [{Cu(dpy)(MeCN)₂}₂{Hg[TeFe₃(CO)₉]₂}]_n (1) was obtained. Single-crystal X-ray diffraction showed that polymer 1 consisted of cationic chains [Cu(dpy)(MeCN)₂]_n and weakly coordinating anions [Hg{TeFe₃(CO)₉}₂]^2–. In contrast, when a sulfur-based cluster was used in a similar ion-exchange reaction, the resulting cross-linked 1D polymer [{Cu(dpy)(MeCN)}₂{Hg[SFe₃(CO)₉]₂}]_n (2) was formed, with the [Hg{SFe₃(CO)₉}₂] moiety serving as a cross-linker via the Cu–S bond. Further, the three-component mechanochemical reactions of [Cu(dpy)(MeCN)₂(BF₄)]_n, chalcogenide clusters [Et₄N]₂[Hg{EFe₃(CO)₉}₂] (E = Te, Se), and dpy in a ratio of 2:1:0.5 produced the unique 1D/2D-hybrid cation–anion polymers [{Cu(dpy)(MeCN)₂}₂{Cu(dpy)_1.5(MeCN)}₂{Hg[EFe₃(CO)₉]₂}₂]_n (E = Te, 3a; Se, 3b), respectively. Notably, polymer 3a could be obtained by the transformation of polymer 1 with dpy via LAG. Detailed single-crystal X-ray analyses revealed extensive weak intermolecular interactions within these polymeric frameworks. Importantly, the cluster-introduced Cu polymers 1, 2, 3a, and 3b possessed low optical energy gaps in a range of 1.36–1.63 eV, which was significantly lower than the parent polymer [Cu(dpy)(MeCN)₂(BF₄)]_n (2.46 eV). Their efficient electron-transport properties were further investigated through density-of-state (DOS) calculations.

Original language	English
Article number	124031
Journal	Journal of Organometallic Chemistry
Volume	1048
DOIs	https://doi.org/10.1016/j.jorganchem.2026.124031
Publication status	Published - 2026 Mar 15

Keywords

Coordination polymers
Mechanochemical syntheses
Metal carbonyl clusters
Weak interactions

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jorganchem.2026.124031

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Li, Y. H., Fu, I. H., Chen, Y. M., Chen, H. L., & Shieh, M. (2026). Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters: Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties. Journal of Organometallic Chemistry, 1048, Article 124031. https://doi.org/10.1016/j.jorganchem.2026.124031

Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters: Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties. / Li, Yu Huei; Fu, I. Hsuan; Chen, Yen Ming et al.
In: Journal of Organometallic Chemistry, Vol. 1048, 124031, 15.03.2026.

Research output: Contribution to journal › Article › peer-review

@article{b381d3a68c444c4d87f9b77f4af0f0fd,

title = "Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters: Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties",

abstract = "Efficient synthetic routes to metal carbonyl cluster–based polymers via ion-exchange processes remain unexplored. In this study, a mechanochemical ion-exchange strategy was developed using a one-dimensional (1D) Cu–dpy (dpy = 4,4{\textquoteright}-dipyridyl) template polymer, [Cu(dpy)(MeCN)2(BF4)]n, and Hg-bridged iron carbonyl chalcogenide clusters, [Et4N]2[Hg\{EFe3(CO)9\}2] (E = Te, Se, S), to construct novel polymeric materials. When polymer [Cu(dpy)(MeCN)2(BF4)]n was treated with [Et4N]2[Hg\{TeFe3(CO)9\}2] in a ratio of 2: 1 via liquid-assisted grinding (LAG), a 1D polymer [\{Cu(dpy)(MeCN)2\}2\{Hg[TeFe3(CO)9]2\}]n (1) was obtained. Single-crystal X-ray diffraction showed that polymer 1 consisted of cationic chains [Cu(dpy)(MeCN)2]n and weakly coordinating anions [Hg\{TeFe3(CO)9\}2]2–. In contrast, when a sulfur-based cluster was used in a similar ion-exchange reaction, the resulting cross-linked 1D polymer [\{Cu(dpy)(MeCN)\}2\{Hg[SFe3(CO)9]2\}]n (2) was formed, with the [Hg\{SFe3(CO)9\}2] moiety serving as a cross-linker via the Cu–S bond. Further, the three-component mechanochemical reactions of [Cu(dpy)(MeCN)2(BF4)]n, chalcogenide clusters [Et4N]2[Hg\{EFe3(CO)9\}2] (E = Te, Se), and dpy in a ratio of 2:1:0.5 produced the unique 1D/2D-hybrid cation–anion polymers [\{Cu(dpy)(MeCN)2\}2\{Cu(dpy)1.5(MeCN)\}2\{Hg[EFe3(CO)9]2\}2]n (E = Te, 3a; Se, 3b), respectively. Notably, polymer 3a could be obtained by the transformation of polymer 1 with dpy via LAG. Detailed single-crystal X-ray analyses revealed extensive weak intermolecular interactions within these polymeric frameworks. Importantly, the cluster-introduced Cu polymers 1, 2, 3a, and 3b possessed low optical energy gaps in a range of 1.36–1.63 eV, which was significantly lower than the parent polymer [Cu(dpy)(MeCN)2(BF4)]n (2.46 eV). Their efficient electron-transport properties were further investigated through density-of-state (DOS) calculations.",

keywords = "Coordination polymers, Mechanochemical syntheses, Metal carbonyl clusters, Weak interactions",

author = "Li, \{Yu Huei\} and Fu, \{I. Hsuan\} and Chen, \{Yen Ming\} and Chen, \{Hui Lung\} and Minghuey Shieh",

note = "Publisher Copyright: {\textcopyright} 2026",

year = "2026",

month = mar,

day = "15",

doi = "10.1016/j.jorganchem.2026.124031",

language = "English",

volume = "1048",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters

T2 - Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties

AU - Li, Yu Huei

AU - Fu, I. Hsuan

AU - Chen, Yen Ming

AU - Chen, Hui Lung

AU - Shieh, Minghuey

PY - 2026/3/15

Y1 - 2026/3/15

N2 - Efficient synthetic routes to metal carbonyl cluster–based polymers via ion-exchange processes remain unexplored. In this study, a mechanochemical ion-exchange strategy was developed using a one-dimensional (1D) Cu–dpy (dpy = 4,4’-dipyridyl) template polymer, [Cu(dpy)(MeCN)2(BF4)]n, and Hg-bridged iron carbonyl chalcogenide clusters, [Et4N]2[Hg{EFe3(CO)9}2] (E = Te, Se, S), to construct novel polymeric materials. When polymer [Cu(dpy)(MeCN)2(BF4)]n was treated with [Et4N]2[Hg{TeFe3(CO)9}2] in a ratio of 2: 1 via liquid-assisted grinding (LAG), a 1D polymer [{Cu(dpy)(MeCN)2}2{Hg[TeFe3(CO)9]2}]n (1) was obtained. Single-crystal X-ray diffraction showed that polymer 1 consisted of cationic chains [Cu(dpy)(MeCN)2]n and weakly coordinating anions [Hg{TeFe3(CO)9}2]2–. In contrast, when a sulfur-based cluster was used in a similar ion-exchange reaction, the resulting cross-linked 1D polymer [{Cu(dpy)(MeCN)}2{Hg[SFe3(CO)9]2}]n (2) was formed, with the [Hg{SFe3(CO)9}2] moiety serving as a cross-linker via the Cu–S bond. Further, the three-component mechanochemical reactions of [Cu(dpy)(MeCN)2(BF4)]n, chalcogenide clusters [Et4N]2[Hg{EFe3(CO)9}2] (E = Te, Se), and dpy in a ratio of 2:1:0.5 produced the unique 1D/2D-hybrid cation–anion polymers [{Cu(dpy)(MeCN)2}2{Cu(dpy)1.5(MeCN)}2{Hg[EFe3(CO)9]2}2]n (E = Te, 3a; Se, 3b), respectively. Notably, polymer 3a could be obtained by the transformation of polymer 1 with dpy via LAG. Detailed single-crystal X-ray analyses revealed extensive weak intermolecular interactions within these polymeric frameworks. Importantly, the cluster-introduced Cu polymers 1, 2, 3a, and 3b possessed low optical energy gaps in a range of 1.36–1.63 eV, which was significantly lower than the parent polymer [Cu(dpy)(MeCN)2(BF4)]n (2.46 eV). Their efficient electron-transport properties were further investigated through density-of-state (DOS) calculations.

AB - Efficient synthetic routes to metal carbonyl cluster–based polymers via ion-exchange processes remain unexplored. In this study, a mechanochemical ion-exchange strategy was developed using a one-dimensional (1D) Cu–dpy (dpy = 4,4’-dipyridyl) template polymer, [Cu(dpy)(MeCN)2(BF4)]n, and Hg-bridged iron carbonyl chalcogenide clusters, [Et4N]2[Hg{EFe3(CO)9}2] (E = Te, Se, S), to construct novel polymeric materials. When polymer [Cu(dpy)(MeCN)2(BF4)]n was treated with [Et4N]2[Hg{TeFe3(CO)9}2] in a ratio of 2: 1 via liquid-assisted grinding (LAG), a 1D polymer [{Cu(dpy)(MeCN)2}2{Hg[TeFe3(CO)9]2}]n (1) was obtained. Single-crystal X-ray diffraction showed that polymer 1 consisted of cationic chains [Cu(dpy)(MeCN)2]n and weakly coordinating anions [Hg{TeFe3(CO)9}2]2–. In contrast, when a sulfur-based cluster was used in a similar ion-exchange reaction, the resulting cross-linked 1D polymer [{Cu(dpy)(MeCN)}2{Hg[SFe3(CO)9]2}]n (2) was formed, with the [Hg{SFe3(CO)9}2] moiety serving as a cross-linker via the Cu–S bond. Further, the three-component mechanochemical reactions of [Cu(dpy)(MeCN)2(BF4)]n, chalcogenide clusters [Et4N]2[Hg{EFe3(CO)9}2] (E = Te, Se), and dpy in a ratio of 2:1:0.5 produced the unique 1D/2D-hybrid cation–anion polymers [{Cu(dpy)(MeCN)2}2{Cu(dpy)1.5(MeCN)}2{Hg[EFe3(CO)9]2}2]n (E = Te, 3a; Se, 3b), respectively. Notably, polymer 3a could be obtained by the transformation of polymer 1 with dpy via LAG. Detailed single-crystal X-ray analyses revealed extensive weak intermolecular interactions within these polymeric frameworks. Importantly, the cluster-introduced Cu polymers 1, 2, 3a, and 3b possessed low optical energy gaps in a range of 1.36–1.63 eV, which was significantly lower than the parent polymer [Cu(dpy)(MeCN)2(BF4)]n (2.46 eV). Their efficient electron-transport properties were further investigated through density-of-state (DOS) calculations.

KW - Coordination polymers

KW - Mechanochemical syntheses

KW - Metal carbonyl clusters

KW - Weak interactions

UR - https://www.scopus.com/pages/publications/105028641495

UR - https://www.scopus.com/pages/publications/105028641495#tab=citedBy

U2 - 10.1016/j.jorganchem.2026.124031

DO - 10.1016/j.jorganchem.2026.124031

M3 - Article

AN - SCOPUS:105028641495

SN - 0022-328X

VL - 1048

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

M1 - 124031

ER -

Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters: Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties

Abstract

Keywords

ASJC Scopus subject areas

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