4.8 Article

Unusual Luminescence Enhancement of Metallogels of Alkynylplatinum(II) 2,6-Bis(N-alkylbenzimidazol-2′-yl)pyridine Complexes upon a Gel-to-Sol Phase Transition at Elevated Temperatures

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 17, Pages 6253-6260

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ja900895x

Keywords

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Funding

  1. The University of Hong Kong
  2. URC Strategic Research Theme on Molecular Materials
  3. RGC Central Allocation Vote (CAV) [HKU 2/05C]
  4. National Natural Science Foundation of China
  5. Research Grants Council of Hong Kong Joint Research Scheme [N_HKU 737/06]

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A series of alkynylplatinum(II) complexes of 2,6-bis(N-alkylbenzimidazol-2'-yl)pyridine has been synthesized and characterized by H-1 NMR, IR, FAB mass spectrometry, and elemental analysis; the photophysical properties have also been investigated. All the complexes have been shown to exhibit interesting gelation properties. Scanning electron microscopy (SEM) of the xerogels showed a network of fibrous structures, typical of morphologies of organogels/metallogels. Interestingly, two of the complexes were found to show strong luminescence enhancement upon a gel-to-sol phase transition upon increasing the temperature. This unusual behavior is rarely encountered, as it represents a sharp contrast to that exhibited by other typical thermotropic organogels and metallogels reported so far. Variable-temperature UV-vis and luminescence spectroscopies were performed to probe the gel-to-sol phase transition. Concentration-dependent, variable-temperature, and time-resolved emission studies in dilute benzene solution have also been made to provide further insights into the spectroscopic origin in the Sol forms. A quantitative treatment of the system based on the Birks scheme has been performed.

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