摘要
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.
原文 | 英語 |
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頁(從 - 到) | 11261-11271 |
頁數 | 11 |
期刊 | Chemistry - A European Journal |
卷 | 23 |
發行號 | 47 |
DOIs | |
出版狀態 | 已發佈 - 2017 8月 22 |
ASJC Scopus subject areas
- 催化
- 有機化學
指紋
深入研究「Semiconducting Coordination Polymers Based on the Predesigned Ternary Te-Fe-Cu Carbonyl Cluster and Conjugation-Interrupted Dipyridyl Linkers」主題。共同形成了獨特的指紋。資料集
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CCDC 1027192: Experimental Crystal Structure Determination
Shieh, M. (Creator), Yu, C. (Creator), Miu, C. (Creator), Kung, C. (Creator), Huang, C. (Creator), Liu, Y. (Creator), Liu, H. (Creator) & Shen, C. (Creator), Unknown Publisher, 2017
DOI: 10.5517/ccdc.csd.cc13gw7p, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc13gw7p&sid=DataCite
資料集: Dataset
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CCDC 1027195: Experimental Crystal Structure Determination
Shieh, M. (Creator), Yu, C. (Creator), Miu, C. (Creator), Kung, C. (Creator), Huang, C. (Creator), Liu, Y. (Creator), Liu, H. (Creator) & Shen, C. (Creator), Unknown Publisher, 2017
DOI: 10.5517/ccdc.csd.cc13gwbs, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc13gwbs&sid=DataCite
資料集: Dataset
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CCDC 1027194: Experimental Crystal Structure Determination
Shieh, M. (Creator), Yu, C. (Creator), Miu, C. (Creator), Kung, C. (Creator), Huang, C. (Creator), Liu, Y. (Creator), Liu, H. (Creator) & Shen, C. (Creator), Unknown Publisher, 2017
DOI: 10.5517/ccdc.csd.cc13gw9r, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc13gw9r&sid=DataCite
資料集: Dataset