Structure-Property Relationships of Inorganic-Organic Hybrid Semiconducting Se-Fe-Cu-CO Polymers

Yu Hsin Liu, Kai Ting Huang, Wei Cheng Chen, Yu Wei Li, Wei Ming Ke, Biing Ruey Ho, Ming Chi Hsu, Yu Huei Li, Minghuey Shieh*

*此作品的通信作者

研究成果: 雜誌貢獻期刊論文同行評審

摘要

A novel family of inorganic-organic-hybrid SeFe3(CO)9-dipyridyl two- and one-dimensional Cu polymers was synthesized via the three-component liquid-assisted grinding (LAG) of [Cu(MeCN)4]+, inorganic cluster [SeFe3(CO)9]2- (1), and rigid conjugated dipyridyls 4,4′-dipyridyl (dpy) and 1,2-bis(4-pyridyl)ethylene (bpee) or flexible conjugation-interrupted dipyridyls 1,2-bis(4-pyridyl)ethane (bpea) and 1,3-bis(4-pyridyl)propane (bpp). They included a cluster-linked 2D polymer, [(μ4-Se)Fe3(CO)9Cu2(MeCN)(dpy)1.5]n (1-dpy-2D), a cluster-pendant 1D chain, [(μ3-Se)Fe3(CO)9Cu2(dpy)3]n (1-dpy-1D), cluster-blocked 1D polymers, [(μ3-Se)Fe3(CO)9Cu2(L)]n (1-L-1D, L = bpee, bpea), and a cluster-linked 2D polymer, [(μ4-Se)Fe3(CO)9Cu2(bpp)2]n (1-bpp-2D). The reversible dimensionality transformations of these three types of polymers accompanied by the change in coordination modes of 1 were achieved by the LAG addition of 1/[Cu(MeCN)4]+ or dipyridyl ligands. These polymers were found to possess tunable low-energy gaps (1.49-1.72 eV) that increased in the order regarding their structural features: cluster-linked 1-dpy-2D and 1-bpp-2D, cluster-blocked 1-bpea-1D and 1-bpee-1D, and cluster-pendant 1-dpy-1D and [(μ3-Se)Fe3(CO)9Cu2(L)2.5]n (L = bpee, 1-bpee-2D; bpea, 1-bpea-2D), indicative of the importance of the participation of cluster 1. The measured electrical conductivities of 1-bpp-2D, 1-bpea-1D, and 1-dpy-1D were 3.13 × 10-7, 2.92 × 10-7, and 2.30 × 10-7 S·cm-1, respectively, which were parallel for the trend in their energy gaps, revealing semiconducting behaviors, supported by XPS, XANES, and DFT calculations. The surprising semiconductivity of the conjugation-interrupted bpp-linked 1-bpp-2D was mainly ascribed to electron transport via C-H···O(carbonyl) hydrogen bonds and aromatic C-H···πcontacts within its closely packed 2D layers. Water-/light-stable polymers 1-bpp-2D, 1-bpea-2D, and 1-dpy-1D were also demonstrated to exhibit excellent pseudo-first-order photodegradation toward nitroaromatics and organic dyes, where cluster-linked polymer 1-bpp-2D performed the best, as predicted by its structural features and narrow energy gap.

原文英語
頁(從 - 到)18270-18282
頁數13
期刊Inorganic Chemistry
60
發行號23
DOIs
出版狀態已發佈 - 2021 12月 6

ASJC Scopus subject areas

  • 物理與理論化學
  • 無機化學

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