TY - JOUR
T1 - Semiconducting Coordination Polymers Based on the Predesigned Ternary Te-Fe-Cu Carbonyl Cluster and Conjugation-Interrupted Dipyridyl Linkers
AU - Shieh, Minghuey
AU - Yu, Chia Chi
AU - Miu, Chia Yeh
AU - Kung, Chang Hung
AU - Huang, Chung Yi
AU - Liu, Yu Hsin
AU - Liu, Hsiang Lin
AU - Shen, Chih Chiang
N1 - Funding Information:
This work was supported by the Ministry of Science and Technology of Taiwan (Grant No. 104–2113-M-003-004-MY3 to M.S.). We thank the NCHC of Taiwan for providing the computer time and the facilities. We also thank the NSRRC of Taiwan for providing the facilities and XAS measurements. Our gratitude also goes to the Academic Paper Editing Clinic, NTNU.
Funding Information:
This work was supported by the Ministry of Science and Technology of Taiwan (Grant No. 104?2113-M-003-004-MY3 to M.S.). We thank the NCHC of Taiwan for providing the computer time and the facilities. We also thank the NSRRC of Taiwan for providing the facilities and XAS measurements. Our gratitude also goes to the Academic Paper Editing Clinic, NTNU.
Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/8/22
Y1 - 2017/8/22
N2 - 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.
AB - 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.
KW - carbonyl ligands
KW - cluster compounds
KW - copper
KW - polymers
KW - through-space interactions
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U2 - 10.1002/chem.201701257
DO - 10.1002/chem.201701257
M3 - Article
C2 - 28497504
AN - SCOPUS:85027863412
VL - 23
SP - 11261
EP - 11271
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 47
ER -