Semiconducting Coordination Polymers Based on the Predesigned Ternary Te-Fe-Cu Carbonyl Cluster and Conjugation-Interrupted Dipyridyl Linkers

Minghuey Shieh, Chia Chi Yu, Chia Yeh Miu, Chang Hung Kung, Chung Yi Huang, Yu Hsin Liu, Hsiang Lin Liu, Chih Chiang Shen

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6 Citations (Scopus)

Abstract

A series of semiconducting cluster-incorporated Cu-based coordination polymers, namely, 1D zigzag polymers [{TeFe3(CO)9Cu2}(L)]n (L=1,2-bis(4-pyridyl)ethane (bpea), 1; L=1,2-bis(4-pyridyl)ethylene (bpee), 5), 2D honeycomb-like polymers [{TeFe3(CO)9Cu}Cu(L)2.5]n (L=bpea, 2; L=bpee, 6), and 2D wave-like cation–anion polymer [{Cu2(L)4}({TeFe3(CO)9Cu}2(L))]n (L=1,3-bis(4-pyridyl)propane (bpp), 4), as well as the macrocycle [{TeFe3(CO)9Cu2}2(bpp)2] (3) have been quantitatively synthesized via the liquid-assisted grinding from the pre-designed cluster [TeFe3(CO)9Cu2(MeCN)2] with conjugated or conjugation-interrupted dipyridyl linkers. Notably, the most conjugation-interrupted bpp-bridged polymer 4 exhibited extraordinary semiconducting characteristics with an ultra-narrow bandgap of 1.43 eV and a DC conductivity of 1.5×10−2 Ω−1 cm−1, which violates our knowledge, mainly attributed to the through-space electron transport via non-classical C−H⋅⋅⋅O(carbonyl) hydrogen bonds and aromatic C−H⋅⋅⋅π interactions. The incorporated Te-Fe-CO anions can not only provide numerous possibilities for secondary interactions within these Cu-based polymers but also serve as a redox-active coordination ligand to promote their conductivities. The intriguing structure–property relationships were studied by X-ray and DFT analyses and further demonstrated by significant change in the oxidation state of Cu atoms by XPS and Cu K-edge XANES.

Original languageEnglish
Pages (from-to)11261-11271
Number of pages11
JournalChemistry - A European Journal
Volume23
Issue number47
DOIs
Publication statusPublished - 2017 Aug 22

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Keywords

  • carbonyl ligands
  • cluster compounds
  • copper
  • polymers
  • through-space interactions

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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