Pseudorotaxane Ligand-Induced Formation of Copper(I)lodide Cluster Based Assembly Materials:From Zero to Three Dimensional

Comprehensive Summary In this work,we have successfully obtained a series of novel copper(I)–iodide clusters(CuI NCs)based assembly materials by combining supramolecular pseudorotaxane ligands{[Mebpe^(+)]PF_(6)^(–)@CB[6](CB[6]=cucurbit[6]uril),L’·PF_(6)}and linkers{BPHF@CB[6],[BPHF=C_(14)H_(20)N_(4)(PF_(6))_(2)],L·PF_(6)},including discrete cluster CuI 1 and extended cluster organic frameworks MORF 1 and MORF 2.CuI 1 can be described as a dumbbell-shaped molecule with its body-centered site and two vertexes respectively occupied by one[Cu_(5)I_(6)]^(–)cluster and two CB[6]held together by two L’·PF_(6) ligands.The crystal structures of MORF 1 and MORF 2 are 1D anionic chain and four-fold interpenetrated 3D cationic diamondoid structure,respectively,which all featured intriguing alternating CB[6]and CuI NCs.

Alkynyl-anchored silver nanoclusters in lanthanide metal-organic framework for luminescent thermometer and CO_(2) cycloaddition

In this study,an alkynyl-modified aromatic dicarboxylic acid bifunctional ligand was selected to construct lanthanide compound{[Eu_(4)(ebdc)_(6)(4,4-bpy)_(0.5)(H_(2)O)_(4.5)]·(C_(2)H_(5)OH)_(1.25)(H_(2)O)}_(n)(Eu-MOF,H_(2)ebdc=5-ethynyl-isophthalic acid,4,4-bpy=4,4-bipyridine,MOF=metal-organic framework),of which the uncoordinated alkynyl group would be used to anchor silver nanoclusters(Ag NCs).The Eu-MOF exhibits double emission peaks,located at 492 and 611 nm,respectively,in which the high-energy blue emission is associated with alkynyl-modified ligand while the low-energy red emission belongs to characteristic emission of Eu3+,indicating that ligands can effectively sensitize Eu3+luminescence.The intensity ratio of the dual emission fluorescence peaks of Eu-MOF displays a good linear relationship with temperature,which realizes the detection function in the low temperature region of 75–275 K,the thermal sensitivity reaches 1.5398%·K^(−1).After anchoring the Ag NCs,the high-energy blue emission is significantly quenched,indicating that the Ag NCs are indeed confined into the framework and interact with the alkynyl group,and thus change the overall electronic distribution.This is the first case of anchoring Ag NCs by a luminescent Eu-MOF and studying nanocluster loading by using spectroscopic properties.In addition,the Ag NCs@Eu-MOF also shows a good catalytic activity for cycloaddition reaction from CO_(2)and epoxides.This study not only provides ideas for exploring the changes in optical properties of luminescent MOFs and Ag NCs caused by confinement effect,but also expands their potential applications in various fields.

Engineering intermolecular charge transfer in chiral organometallic crystals by rational doping for high-contrast CPL switches

The development of circularly polarized luminescence(CPL)switches is of great importance but challenging.Herein,a charge donor/acceptor pair comprising two chiral gold(I)-isocyanide complexes was designed to construct light-harvesting system via intermolecular charge-transfer(CT)interactions.By doping nonemissive S-Au I into blue-emitting S-AuCN,(S-Au CN)_(1-x)(S-AuI)_(x)(0≤x≤3.4%)with tunable emission from blue to red was achieved.This large red-shifted emission was realized based on the remarkable change of the electronic properties between the S-Au CN dimer and red-emitting(S-A CN)-(S-AuI)CT pair,and the resulting energy-transfer(En T)process between them.Importantly,the En T process can be switched off/on by external stimuli of grinding and CH_(2)Cl_(2)fuming,giving rise to high-contrast(blue versus red)CPL switching properties.This study opens a novel avenue for developing CPL switches by constructing light-harvesting CT-doped systems based on chiral organometallic complexes.

Luminescence modulation of ultrasmall gold clusters by aromatic ligands

Luminescence is one of the most important properties for metal nanoclusters;however,clearly revealing its origin remains challenging.The different luminescence properties of the two prototypical 8e nanoclusters Au_(11)and Au_(13)remain elusive—Au_(11)is always nonluminescent,whereas Au_(13)is luminescent.In this work,by using a designed unique aromatic ligand(quinoline-2-thiol),we obtained new atomically precise phosphine-thiolate-protected neutral Au_(11)-SH and cationic Au_(13)-SH.In comparison with the classic phosphine-halide-protected Au_(11)-Cl and Au_(13)-Cl,the Cl-to-thiol alteration triggered room-temperature luminescence of the Au_(11)core and dramatically modulated that of the Au_(13)core.Ultrafast ultraviolet/infrared(UV/IR)spectroscopy,which is sensitive to organic aromatic groups,together with ultrafast transient absorption(TA)spectroscopy unprecedently revealed a relaxation process from the ligand to core state affecting the dynamics in excited states and some critical intermediate states favouring efficient room-temperature emission of these nanoclusters.This work provides some new insights into the origin of photoluminescence of metal nanoclusters and opens an avenue to modulate the dynamics of their excited states using aromatic ligands,which would have direct applications in lighting,light harvesting,and photocatalysis.

An efficient and versatile biopolishing strategy to construct high performance zinc anode

Conventional strategies for highly reversible Zn anodes usually involve complex and time-consuming production processes of current collectors,expensive and toxic electrolyte additives,or the introduction of inactive materials in protective layer.Here,we develop a fast,facile,and environmentally friendly biopolishing method to prepare dendrite-free Zn anodes,which merely involves the simple immersion of Zn foil in a biocompatible cysteine aqueous solution.The ravine structure formed by sulfhydryl etching for 30 min not only increases the electroactive area of Zn anode but also regulates the distribution of electric field and Zn ions,ensuring the homogeneous deposition and stripping of Zn ions.The biopolished Zn anode can be operated steadily for 2,000 h with a low voltage hysteresis at a current density of 1 mA·cm^(−2).In addition,Zn anodes with a cycle life of 500 h can be built by soaking for only 5 min,proving the high efficiency of the proposed method.This strategy is generalized to substances with sulfhydryl groups for polishing Zn electrodes with improved performance.The cysteine-polished Zn//activated carbon supercapacitor can stably run for 20,000 cycles without obvious capacity attenuation.The proposed strategy shows potential for producing advanced Zn anodes.

Circularly polarized luminescence of agglomerate emitters

Circularly polarized luminescence(CPL)originates from the chiral emissive excited states.CPL materials have promising applications in 3D optical displays,encryptions,biological probes,chiral photoelectric devices,and CPL switches,most of which require excellent CPL performances including bright luminescence and high luminescence dissymmetry factor(glum)in the agglomerate state.This review systematically summarizes the progress about CPL of aggregate and solid materials,such as organic materials,metal-organic materials(such as coordination polymers,organic-inorganic metal halides,metal clusters,and cluster-assembled materials),the assembled materials by supramolecular interactions,and liquid crystals.We also present the current challenges and a future perspective of chiral emitting agglomerate materials.

Evolution of all-carboxylate-protected superatomic Ag clusters confined in Ti-organic cages

In this study,the size of the titanium organic cage was controlled to achieve the restricted growth from a single Ag(I)atom(Ag@Ti_(5))to rare all-carboxylate-protected superatomic Ag cluster(Ag6@Ti_(6)).The classical octahedral Ag_(6)^(4+) cluster with two delocalized electrons(2e)has been encapsulated in a Ti6 organic cage,which shows high stability in air and dimethyformamide(DMF).Furthermore,larger 2e nested double-tetrahedra Ag clusters(Ag_(8)^(6+) and Ag_(9)^(7+))protected using a tetrahedral hollow metalloligand framework(Ag_(8)@Ti_(4) and Ag_(9)@Ti_(4))were obtained.Electrospray ionization mass spectrometry(ESI-MS)and density functional theory(DFT)calculations confirmed that there are two delocalized electrons on these small Ag clusters.This study provides a new form of protection for superatomic Ag clusters and provides a feasible strategy for the development of stable Ag clusters.