Electronic, Optical, and Computational Studies of a Redox-Active Napthalenediimide-Based Coordination Polymer

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• 作者：Chanel F. Leong ; Bun Chan ; Thomas B. Faust ; Peter Turner ; Deanna M. D鈥橝lessandro
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：December 16, 2013
• 年：2013
• 卷：52
• 期：24
• 页码：14246-14252
• 全文大小：334K
• 年卷期：v.52,no.24(December 16, 2013)
• ISSN：1520-510X

文摘

The new one-dimensional coordination framework (Zn(DMF)NO₃)₂(NDC)(DPMNI), where NDC = 2,6-naphthalenedicarboxylate and DPMNI = N,N鈥?bis(4-pyridylmethyl)-1,4,5,8-naphthalenetetracarboxydiimide, which has been crystallographically characterized, exhibits two redox-accessible states due to the successive reduction of the naphthalenediimide (NDI) ligand core. Solid-state electrochemical and vis鈥搉ear-IR spectroelectrochemical measurements coupled with density functional theory (DFT) calculations enabled the origins of the optical transitions in the spectra of the monoradical anion and dianion states of the material to be assigned. Electron paramagnetic resonance (EPR) spectroscopy revealed that the paramagnetic radical anion state of the DPMNI core could be accessed upon broad-spectrum white light irradiation of the material, revealing a long-lived excited state, possibly stabilized by charge delocalization which arises from extensive 蟺鈥?/i>蟺* stacking interactions between alternating NDC and NDI aromatic cores which are separated by a distance of 3.580(2) 脜.