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Semiconducting Coordination Polymers Based on the Predesigned Ternary Te‐Fe‐Cu Carbonyl Cluster and Conjugation‐Interrupted Dipyridyl Linkers
Author(s) -
Shieh Minghuey,
Yu ChiaChi,
Miu ChiaYeh,
Kung ChangHung,
Huang ChungYi,
Liu YuHsin,
Liu HsiangLin,
Shen ChihChiang
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701257
Subject(s) - crystallography , xanes , polymer , conjugated system , propane , ternary operation , cluster (spacecraft) , chemistry , oxidation state , ligand (biochemistry) , materials science , polymer chemistry , metal , organic chemistry , spectroscopy , biochemistry , physics , receptor , quantum mechanics , computer science , programming language
A series of semiconducting cluster‐incorporated Cu‐based coordination polymers, namely, 1D zigzag polymers [{TeFe 3 (CO) 9 Cu 2 }(L)] n (L=1,2‐bis(4‐pyridyl)ethane (bpea), 1 ; L=1,2‐bis(4‐pyridyl)ethylene (bpee), 5 ), 2D honeycomb‐like polymers [{TeFe 3 (CO) 9 Cu}Cu(L) 2.5 ] n (L=bpea, 2 ; L=bpee, 6 ), and 2D wave‐like cation–anion polymer [{Cu 2 (L) 4 }({TeFe 3 (CO) 9 Cu} 2 (L))] n (L=1,3‐bis(4‐pyridyl)propane (bpp), 4 ), as well as the macrocycle [{TeFe 3 (CO) 9 Cu 2 } 2 (bpp) 2 ] ( 3 ) have been quantitatively synthesized via the liquid‐assisted grinding from the pre‐designed cluster [TeFe 3 (CO) 9 Cu 2 (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.