期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 12, 页码 4111-4118出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja511713c
关键词
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资金
- DOE [DE-AC02-06CH11357]
- NIH [RO1 CA133697]
- Defense Threat Reduction Agency [HDTRA1-13-1-0046]
- Joint Center of Excellence in Integrated Nanosystems (JCIN) at King Abdul-Aziz City for Science and Technology (KACST) [34-949]
- Northwestern University (NU)
- Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center - DOE, Office of Science, Office of Basic Energy Sciences [DE-SC0001059]
- China Scholarship Council (CSC)
- National Science Council of the People's Republic of China [21271026]
- Ryan Fellowship under NU International Institute for Nanotechnology (IIN)
Although complexation of hydrophilic guests inside the cavities of hydrophobic hosts is considered to be unlikely, we demonstrate herein the complexation between gamma- and beta-cyclodextrins (gamma- and beta-CDs) with an archetypal polyoxometalate (POM)-namely, the [PMo12O40](3-) trianion-which has led to the formation of two organic-inorganic hybrid 2:1 complexes, namely [La(H2O)(9)]{[PMo12O40]subset of[gamma-CD](2)} (CD-POM-1) and [La(H2O)(9)] {[PMo12O40]subset of[beta-CD](2)} (CD-POM-2), in the solid state. The extent to which these complexes assemble in solution has been investigated by (i) H-1, C-13, and P-31 NMR spectroscopies and (ii) small- and wide-angle X-ray scattering, as well as (iii) mass spectrometry. Single-crystal X-ray diffraction reveals that both complexes have a sandwich-like structure, wherein one [PMo12O40](3-) trianion is encapsulated by the primary faces of two CD tori through intermolecular [C-H center dot center dot center dot O-Mo] interactions. X-ray crystal superstructures of CD-POM-1 and CD-POM-2 show also that both of these 2:1 complexes are lined up longitudinally in a one-dimensional columnar fashion by means of [O-H center dot center dot center dot O] interactions. A beneficial nanoconfinement-induced stabilizing effect is supported by the observation of slow color changes for these supermolecules in aqueous solution phase. Electrochemical studies show that the redox properties of [PMo12O40](3-) trianions encapsulated by CDs in the complexes are largely preserved in solution. The supramolecular complementarity between the CDs and the [PMo12O40](3-) trianion provides yet another opportunity for the functionalization of POMs under mild conditions by using host-guest chemistry.
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