4.8 Article

Rhodamine 6G-Labeled Pyridyl Aroylhydrazone Fe(II) Complex Exhibiting Synergetic Spin Crossover and Fluorescence

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 30, Pages 9426-9433

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b00103

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Funding

  1. National Natural Science Foundation of China [21571113, 21771115]
  2. 973 program [2013CB933403]
  3. MEXT KAKENHI [17H01197]
  4. China Scholarship Council

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Here, we use a pyridinecarbaldehyde rhodamine 6G hydrazone ligand (L) to synthesize an Fe(II) complex 1 for the search of new fluorescent-spin crossover (SCO) materials. Single-crystal structural determinations suggest that the Fe(II) ion is chelated by two ring-opened ligands (L-o) to form a FeN4O2 coordination environment, and intermolecular pi---pi contacts of the xanthene groups connect the adjacent molecules to form a supramolecular one-dimensional chain. Magnetic susceptibility measurements on complex 1 show that three-step SCO takes place in the temperature range of 120-350 K, and its desolvated form 1-d exhibits SCO around room temperature (T-c up arrow = 343 K and T-c down arrow = 303 K) with a wide hysteresis loop of 40 K. Moreover, complex 1-d displays light-induced excited spin-state trapping phenomenon. Intriguingly, the fluorescence intensity of the maximum emission at 560 nm for complex 1-d displays discontinuous variation in the range of 250-400 K, indicative of the occurrence of synergetic fluorescence and SCO.

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