DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Direct Observation of Node-to-Node Communication in Zeolitic Imidazolate Frameworks

Journal Article · · Journal of the American Chemical Society

Zeolitic imidazolate frameworks (ZIFs) with open-shell transition metal nodes represent a promising class of highly ordered light harvesting antennas for photoenergy applications. However, their charge transport properties within the framework, the key criterion to achieve efficient photoenergy conversion, are not yet explored. Herein, we report the first direct evidence of a charge transport pathway through node-to-node communication in both ground state and excited state ZIFs using the combination of paramagnetic susceptibility measurements and time-resolved optical and X-ray absorption spectroscopy. These findings provide unprecedented new insights into the photoactivity and charge transport nature of ZIF frameworks, paving the way for their novel application as light harvesting arrays in diverse photoenergy conversion devices.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1484204
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 37; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

References (34)

Lessons from nature about solar light harvesting journal September 2011
Concentration Dependent Dimensionality of Resonance Energy Transfer in a Postsynthetically Doped Morphologically Homologous Analogue of UiO-67 MOF with a Ruthenium(II) Polypyridyl Complex journal June 2015
The Chemistry and Applications of Metal-Organic Frameworks journal August 2013
Metal–organic frameworks for artificial photosynthesis and photocatalysis journal January 2014
Metal–Organic Frameworks for Light Harvesting and Photocatalysis journal November 2012
Introduction to Metal–Organic Frameworks journal September 2011
Tuning the structure and function of metal–organic frameworks via linker design journal January 2014
Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks journal September 2011
Amplified Luminescence Quenching of Phosphorescent Metal–Organic Frameworks journal February 2012
Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal–Organic Frameworks journal December 2012
Energy Transfer Dynamics in Metal−Organic Frameworks journal September 2010
Photosensitizing Metal–Organic Framework Enabling Visible-Light-Driven Proton Reduction by a Wells–Dawson-Type Polyoxometalate journal February 2015
Photophysical Characterization of a Ruthenium(II) Tris(2,2′-bipyridine)-Doped Zirconium UiO-67 Metal–Organic Framework journal April 2014
Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H 2 Evolution journal February 2018
Light-Harvesting Metal–Organic Frameworks (MOFs) Efficient Strut-to-Strut Energy Transfer in Bodipy and Porphyrin-Based MOFs journal October 2011
Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks journal January 2010
Zeolitic imidazolate framework materials: recent progress in synthesis and applications journal January 2014
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks journal June 2006
Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application journal November 2017
Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications journal June 2016
Photoactive Zeolitic Imidazolate Framework as Intrinsic Heterogeneous Catalysts for Light-Driven Hydrogen Generation journal December 2016
Electronic Structure Modulation of Metal–Organic Frameworks for Hybrid Devices journal December 2014
Modelling a Linker Mix-and-Match Approach for Controlling the Optical Excitation Gaps and Band Alignment of Zeolitic Imidazolate Frameworks journal November 2016
Electronic Chemical Potentials of Porous Metal–Organic Frameworks journal February 2014
Electrically Conductive Porous Metal-Organic Frameworks journal January 2016
Electronic structure design for nanoporous, electrically conductive zeolitic imidazolate frameworks journal January 2017
Tandem Postsynthetic Metal Ion and Ligand Exchange in Zeolitic Imidazolate Frameworks journal June 2012
Metal-Substituted Zeolitic Imidazolate Framework ZIF-108: Gas-Sorption and Membrane-Separation Properties journal July 2014
Cu 2+ -doped zeolitic imidazolate frameworks (ZIF-8): efficient and stable catalysts for cycloadditions and condensation reactions journal January 2015
Tetrahedral Copper(II) Complexes with a Labile Coordination Site Supported by a Tris-tetramethylguanidinato Ligand journal July 2017
Synthesis, Structure, and Reactivity of Model Complexes of Copper Nitrite Reductase journal January 1996
Spectroscopic Methods in Bioinorganic Chemistry:  Blue to Green to Red Copper Sites journal October 2006
EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu–sulfur complexes journal November 2013
Magnetochemistry book January 1986

Cited By (3)

Switching on the Photocatalysis of Metal–Organic Frameworks by Engineering Structural Defects journal July 2019
Switching on the Photocatalysis of Metal–Organic Frameworks by Engineering Structural Defects journal August 2019
Enhanced light harvesting ability in zeolitic imidazolate frameworks through energy transfer from CdS nanowires journal January 2020