Designed Assembly of Heterometallic Cluster Organic Frameworks Based on Anderson‐Type Polyoxometalate Clusters

The visible‐light‐driven hydrogen evolution reaction (HER) by covalent photosensitizer–catalyst dyads is one of the most elegant concepts in supramolecular homogeneous solar energy conversion. The intricacies of catalyst reactivity and photosensitizer–catalyst interactions require a detailed fundamental understanding of the system to rationalize the observed reactivities. Here, we report three dyads based on the covalent imine‐bond linkage of an iridium photosensitizer and an organo‐functionalized Anderson polyoxometalate anion [MMo6O18{(OCH2)3CNH2}2]3− (M=Mn3+, Fe3+, Co3+). Modification of the central metal ion M is used to modulate the HER activity. Detailed theoretical and experimental studies examine the role of the central metal ion M and provide critical understanding of the redox activity and light‐driven HER activity of the novel dyads. Thus, the study enables a knowledge‐based optimization of HER dyads by chemical modification of the reactive metal oxide components.

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Investigation of the Light‐Driven Hydrogen Evolution by Polyoxometalate–Photosensitizer Dyads

Schönweiz

Heiland

Anjass

et al. 2017

“…While there are several examples of coordination polymers made from preformed clusters, multi‐cluster frameworks derived from polynuclear metalloligands are particularly rare. In fact, the use of cluster‐based metalloligands to form mixed‐cluster assemblies has been dominated by polyoxometallates (POMs) and other metal‐oxide based synthons …”

Section: Figurementioning

confidence: 99%

Stepwise Assembly of an Electroactive Framework from a Co₆S₈ Superatomic Metalloligand and Cuprous Iodide Building Units

Freeman

Edokobi

Gillen

et al. 2020

The design of metal-organic frameworks (MOFs) that incorporate more than one metal cluster constituent is ac hallenging task. Conventionalo ne-pot reactionp rotocols requirej udiciouss election of ligand and metal ion precursors, yet remainu npredictable. Stable, preformed nanoclusters, with ligand shells that can undergo additional coordination-driven reactions, provide ap latform for assembling multi-cluster solids with precision.H erein, ad iscrete Co 6 S 8 (PTA) 6 (PTA = 1,3,5-triaza-7-phosphaadamantane) superatomic-metalloligand is assembled into a three-dimensional (3D) coordination polymer comprising Cu 4 I 4 secondary building units (SBUs). The resulting heterobimetallic framework (1)c ontains two distinct cluster constituents and bifunctional PTAl inkers. Solid-state diffuse reflectances tudies revealt hat 1 is an optical semiconductor with ab and-gap of 1.59 eV.F ramework-modified electrodes exhibit reversible redox behaviori nt he solid state arising from the Co 6 S 8 superatoms, which remain intact during framework synthesis.

“…Instead of DABCO and cyclodiphosphazanes, an organic–inorganic hybrid POM, that is, [MnMo 6 O 18 L 2 ] 3− [H 3 L=2‐(hydroxymethyl)‐2‐(pyridin‐4‐yl)‐1,3‐propanediol], is used by the Wang group to assemble with Cu 4 I 4 to form ZCOFs (Figure ) . The [MnMo 6 O 18 L 2 ] 3− POM ligand can be described as a well‐known B‐type Anderson‐type [MnMo 6 O 24 ] 3− cluster capped by two deprotonated L ligands on both sides.…”

Section: Design and Synthesis Of Zcofsmentioning

confidence: 99%

Recent Advances in Zeolite‐like Cluster Organic Frameworks

Lin

Zhao

et al. 2018

Self Cite

During the past decade, research on the design and synthesis of zeolite-like metal-organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite-like cluster organic frameworks (ZCOFs) built from 4-connected metal-cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra-large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite-like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal-halide cluster SBUs, 2) ZCOFs based on metal-oxygen cluster SBUs, 3) ZCOFs based on metal-chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal-cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed.