Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex
- Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, United States
In this study, a method is described here by which to dope ruthenium(II) bis(2,2'-bipyridine) (2,2'-bipyridyl-5,5'-dicarboxylic acid), RuDCBPY, into a UiO-67 metal–organic framework (MOF) derivative in which 2,2'-bipyridyl-5,5'-dicarboxylic acid, UiO-67-DCBPY, is used in place of 4,4'-biphenyldicarboxylic acid. Emission lifetime measurements of the RuDCBPY triplet metal-to-ligand charge transfer, 3MLCT, excited state as a function of RuDCBPY doping concentration in UiO-67-DCBPY are discussed in light of previous results for RuDCBPY-UiO-67 doped powders in which quenching of the 3MLCT was said to be due to dipole–dipole homogeneous resonance energy transfer, RET. The bulk distribution of RuDCBPY centers within MOF crystallites are also estimated with the use of confocal fluorescence microscopy. In the present case, it is assumed that the rate of RET between RuDCBPY centers has an r–6 separation distance dependence characteristic of Förster RET. The results suggest (1) the dimensionality in which RET occurs is dependent on the RuDCBPY concentration ranging from one-dimensional at very low concentrations up to three-dimensional at high concentration, (2) the occupancy of RuDCBPY within UiO-67-DCBPY is not uniform throughout the crystallites such that RuDCBPY densely populates the outer layers of the MOF at low concentrations, and (3) the average separation distance between RuDCBPY centers is ~21 Å.
- Research Organization:
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- SN20074; SC0012446
- OSTI ID:
- 1185241
- Alternate ID(s):
- OSTI ID: 1454259
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 137 Journal Issue: 25; ISSN 0002-7863
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
Similar Records
Insight into Metal–Organic Framework Reactivity: Chemical Water Oxidation Catalyzed by a [Ru(tpy)(dcbpy)(OH 2 )] 2+ ‐Modified UiO‐67
Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film