Selective uptake and removal of aromatic and heterocyclic compounds by para-dicyanobenzene-linked, EFe3(CO)9-incorporated (E = Te, Se), semiconducting Cu chain polymers

Minghuey Shieh*, Yu Huei Li, Yun Huai Chang, Kai Siang Lu, Chien Nan Lin, Biing Ruey Ho

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The uptake and removal of volatile and toxic organic compounds is an important issue in modern industrial chemistry because these organic pollutants have long-term effects on public health and the global environment. In this work, we successfully synthesized two novel para-dicyanobenzene (p-DCB)-linked, EFe3(CO)9-incorporated (E = Te, Se) 1D polymers [EFe3(CO)9Cu2(p-DCB)1.5]n (E = Te, 1a; Se, 1b) from liquid-assisted grinding (LAG) of the di-Cu compounds [EFe3(CO)9Cu2(MeCN)2] with p-DCB. Polymers 1a and 1b had isomorphous structures with single- and double-p-DCB linkers alternatively connected to Cu atoms of EFe3(CO)9Cu2 (E = Te, Se) cores, in which two p-DCB of the double-p-DCB moiety were parallel-displaced with the π···π interaction on their benzene rings. The selective adsorption of C7−C10-alkyl aromatics, polycyclic aromatics, and heterocyclic compounds by 1a and 1b was accomplished via neat grinding or THF-aided LAG processes. These reactions led to the formation of the guest molecule (G)-intercalated products, i.e., 1a- and 1b-based polymers [EFe3(CO)9Cu2(p-DCB)1.5·(G)m]n [E = Te, 1a·mG; E = Se, 1b·mG; m = 0.5 or 1] and the THF-introduced single-p-DCB-bridged polymer [TeFe3(CO)9Cu2(p-DCB)·(THF)]n (2a·1THF). These adsorption activities of 1a and 1b were thoroughly evaluated by single-crystal and powder X-ray analysis and TGA and DSC measurement, where some C−H···π, π···π, and C−H···E (E = O, S) interactions between guest molecules and the p-DCB linkers were observed to stabilize polymer chains. The desorption of volatile heterocyclic (THF, furan, thiophene) or alkyl aromatic (toluene, m-xylene, mesitylene, durene) guest molecules to give the parent polymers 1a and 1b could be achieved by vacuum and recrystallization or stepwise LAG process in the Te system. Importantly, these EFe3(CO)9Cu2-incorporated (E = Te, Se) polymers 1a and 1b, as well as their host−guest adducts, exhibited semiconducting behaviors possessing tunable energy gaps (1.36−1.51 eV) with moderate electrical conductivities ((1.21−6.55)×10–7 S·cm–1), in which the guest molecules played a crucial role in modulating the electron transport in the solid state.

Original languageEnglish
Article number122884
JournalJournal of Organometallic Chemistry
Volume1001
DOIs
Publication statusPublished - 2023 Nov 15

Keywords

  • Coordination polymers
  • Ligands
  • Metal clusters
  • Volatile and toxic organic compounds

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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