Inorganic–organic hybrid Cu–dipyridyl semiconducting polymers based on the redox-active cluster [SFe3(CO)9]2−: filling the gap in iron carbonyl chalcogenide polymers

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作   者：

Hsu Ming-Chi;  Lin Ru Yan;  Sun Tzu-Yen;  Huang Yu-Xin;  Li Min-Sian;  Li Yu-Huei;  Chen Hui-Lung;  Shieh Minghuey; 

作者机构：

National Taiwan Normal University;  Chinese Culture University; 

期刊名称：

Dalton transactions: An international journal of inorganic chemistry

i s s n：

1477-9226

年卷期：

2024 年 53 卷 17 期

页   码：

7303-7314

页   码：

摘   要：

The construction of sulfur-incorporated cluster-based coordination polymers was limited and underexplored due to the lack of efficient synthetic routes. Herein, we report facile mechanochemical ways toward a new series of SFe3(CO)9-based dipyridyl–Cu polymers by three-component reactions of [Et4N]2[SFe3(CO)9] ([Et4N]2[1]) and [Cu(MeCN)4][BF4] with conjugated or conjugation-interrupted dipyridyl ligands, 1,2-bis(4-pyridyl)ethylene (bpee), 1,2-bis(4-pyridyl)ethane (bpea), 4,4′-dipyridyl (dpy), or 1,3-bis(4-pyridyl)propane (bpp), respectively. X-ray analysis showed that bpee-containing 2D polymers demonstrated unique SFe3(CO)9 cluster-armed and cluster-one-armed coordination modes via the hypervalent μ5-S atom. These S–Fe–Cu polymers could undergo flexible structural transformations with the change of cluster bonding modes by grinding with stoichiometric amounts of dipyridyls or 1/[Cu(MeCN)4]+. They exhibited semiconducting behaviors with low energy gaps of 1.55–1.79 eV and good electrical conductivities of 3.26 × 10−8–1.48 × 10−6 S cm−1, tuned by the SFe3(CO)9 cluster bonding modes accompanied by secondary interactions in the solid state. The electron transport efficiency of these polymers was further elucidated by solid-state packing, X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), density of states (DOS), and crystal orbital Hamilton population (COHP) analysis. Finally, the solid-state electrochemistry of these polymers demonstrated redox-active behaviors with cathodically-shifted patterns compared to that of [Et4N]2[1], showing that their efficient electron communication was effectively enhanced by introducing 1 and dipyridyls as hybrid ligands into Cu+-containing networks.