Ming-Liang Tong

Sun Yat-Sen University | SYSU · Shool of Chemistry

A series of heterometallic [Ln(III)xCu(II)y] complexes, [Gd2Cu2]n (1), [Gd4Cu8] (2), [Ln9Cu8] (Ln=Gd, 3⋅Gd; Ln=Dy, 3⋅Dy), were successfully synthesized by a one-pot route at room temperature with three kinds of in situ carbonyl-related reactions: Cannizzaro reaction, aldol reaction, and oxidation. This strategy led to dysprosium analogues that beha...

The relaxation time under zero field reflects the memory retention capabilities of single‐molecule magnets (SMMs) when used as storage devices. Intermolecular magnetic dipole interaction is ubiquitous in aggregates of magnetic molecules and can greatly influence relaxation times. However, such interaction is often considered harmful and challenging...

Spin crossover (SCO) materials with new architectures will expand and enrich the research in the SCO field. Here, we report two metal‐organic frameworks (MOFs) containing tetradentate organic ligands and hexatopic linkers [Ag8X8(CN)6]6− (X = Br and I), which represents the first SCO MOF with clusters as building blocks. The silver halide cluster ca...

Spin crossover (SCO) materials with new architectures will expand and enrich the research in the SCO field. Here, we report two metal‐organic frameworks (MOFs) containing tetradentate organic ligands and hexatopic linkers [Ag8X8(CN)6]6− (X = Br and I), which represents the first SCO MOF with clusters as building blocks. The silver halide cluster ca...

Lanthanide doping is an effective strategy for modulating the emission of emitters. Herein, by changing the cluster composition to control the energy transfer pathway, the application potential of high-nuclearity lanthanide cluster (HLC) as white-light emitter has been confirmed for the first time. Specifically, by precisely controlling the proport...

A dual-switching spin crossover metal-organic framework (SCO-MOF) [Fe(TPB){PtII(CN)4}]·3iPrOH·4H2O (TPB = 1,2,4,5-tetra(pyridin-4-yl)benzene) is developed via the combination of redox-active framework and tunable guests. The reversible structural transformation between [PtII(CN)4]2− and [PtIVBr2(CN)4]2− moieties can be manipulated by redox post-syn...

In the field of molecular magnetism, the lanthanide-radical (Ln-Rad) method has become one of the most appealing tactics for introducing strong magnetic interactions and has spurred on the booming development of heterospin single-molecule magnets (SMMs). The article is a timely retrospect on the research progress of Ln-Rad heterospin systems and sp...

The first germole-ligated single-molecule magnets are reported, with contrasting properties found for the near-linear sandwich complexes [(η8-COT)Ln(η5-CpGe]-, where Ln = Dy (1Dy) or Er (1Er), COT is cyclo-octatetraenyl and CpGe is [GeC4-2,5-(SiMe3)2-3,4-Me2]2-. Whereas 1Er has an energy barrier of 120(1) cm-1 in zero applied field and open hystere...

Magnetically switchable molecular solids with stimuli-responsive ON/OFF characteristics are promising candidates for smart switches and magnetic storage. In addition to conventional spin-crossover/charge-transfer materials whose magnetic responses arise from changes in the electronic structure of the metal centers, peripheral chemical entities that...

Crystal-field symmetry of lanthanide ions plays a critical role in suppressing quantum tunneling of magnetization (QTM) in single-molecule magnets (SMMs), but high-performance SMM design and modulation remain challenging only in view of the geometric symmetry of the first coordination sphere. Herein, two bis(semicarbazone)/bis(thiosemicarbazone)dys...

High-nuclear lanthanide clusters have shown great potential for the administration of high-dose mononuclear gadolinium chelates in magnetic resonance imaging (MRI). The development of high-nuclear lanthanide clusters with excellent solubility and high stability in water or solution has been challenging and is very important for expanding the perfor...

Herein, hexaazamacrocyclic ligand LN6 was employed to construct a series of photochromic rare-earth complexes, [Ln(LN6)(NO3)2](BPh4) [1-Ln, Ln = Dy, Tb, Eu, Gd, Y; LN6 = (3E,5E,10E,12E)-3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane-3,5,10,12-tetraene]. The behavior of photogenerated radicals of hexaazamacrocyclic ligands was revealed fo...

Lanthanide complexes are among the most active frontiers of functional coordination chemistry, especially due to their fascinating magnetic and optical properties. Among them, a hexadentate mixed ligand, H2bbpen, gave birth to some of the best lanthanide single-molecule magnets and photoluminescence complexes. Here we review the coordination chemis...

By incorporating diprotonated terpyridine cation and hexacyanometalate(III) anions into supramolecular hybrid salts, room temperature Photoinduced electron transfer (PET) was achieved with the involvement of [MIII(CN)6]3− (M = Fe, Co) ion....

Spin crossover (SCO) complexes capable of exhibiting distinct spin states under external stimuli have aroused intensive interests in material science. Herein, we report a reverse Hofmann-type metal−organic framework (MOF) [FeII(TPPE){AuI(CN)2}]I·2H2O·7TCE...

In recent years, very significant progress has been made in single-molecule magnets (SMMs), and one of the major milestone works is the hysteresis blocking temperature beyond the boiling point of...

Metal-organic frameworks (MOFs) provide versatile platforms to construct multi-responsive materials. Herein, by introducing the neutral tetradentate ligand and the linear dicyanoaurate(I) anion, we reported a rare cationic MOF [FeII(TPB){AuI(CN)2}]I·4H2O·4DMF (TPB = 1,2,4,5-tetra(pyridin-4-yl)benzene) with hysteretic spin-crossover (SCO) behavior n...

The promising future of storing and processing quantized information at the molecular level has been attracting the study of Single-Molecule Magnets (SMMs) for almost three decades. Although some recent breakthroughs are mainly about the SMMs containing only one lanthanide ion, we believe SMMs can tell a much deeper story than the single-ion anisot...

Linkage isomers involving changes in the bonding mode of ambidentate ligands have potential applications in data storage, molecular machines, and motors. However, the observation of the cyanide-linkage-isomerism-induced spin change (CLIISC) effect characterized by single-crystal X-ray diffraction remains a considerable challenge. Meanwhile, the hig...

Triggered by thermally assisted intermolecular motion via hydrogen bonds, a CoII compound undergoes a single-crystal-to-single-crystal phase transition near room temperature, accompanied by reversible switching of Jahn–Teller distortion, magnetic anisotropy and magnetodielectric effect. Abstract Introducing magnetic switchability into artificial m...

Introducing magnetic switchability into artificial molecular machines is fascinating for precise control of magnetism via external stimuli. Herein, a field‐induced Co II single‐molecule magnet was found to exhibit the reversible switch of Jahn‐Teller distortion near room temperature, along with thermal conformational motion of the 18‐crown‐6 rotor,...

Through a mixed-ligand strategy, the structural change from a discrete dinuclear DyIII cluster to a one-dimensional polymeric chain was achieved, maintaining the two magnetic entities with the same {Dy(dppbO2)2(H2O)5} (dppbO2 = 1,4-butylenebis(diphenylphosphine oxide)) core structure. Since the hydrogen bonding between the equatorial coordinated wa...

Magnetic bistability in single-molecule magnets (SMMs) is a potential basis for new types of nanoscale information storage material. The standard model for thermally activated relaxation of the magnetization in SMMs is based on the occurrence of a single Orbach process. Here, we show that incorporating a phosphorus atom into the framework of the dy...

In this issue of Chem, Demir and colleagues report on the synthesis, ab initio calculations, and magnetic behaviors of two organometallic lanthanide bismuth clusters involving an unprecedented Bi6⁶⁻ Zintl ion. The serendipitous finding sheds light on the design strategies of exchange-coupled single-molecule magnets.

The pursuit of spin crossover (SCO) materials with photoswitchable multistability is driven by fascinating perspectives toward light-response switches and opto-magnetic memory devices. Herein, we report a 3D Hofmann-type metal-organic framework [Fe(bpn){Ag(CN)2}2]·1.5(Fnaph) (bpn = 1,4-di(pyridin-4-yl)naphthalene, Fnaph = 1-fluoronaphthalene), whic...

By employing cyanoborohydride and isomeric tetrapyridyl benzene ligands, a new three-dimensional (3D) [Fe(3-tpb)(NCBH3)2] (1·2H2O, 3-tpb = 1,2,4,5-tetra(pyridin-3-yl)benzene) and a two-dimensional (2D) [Fe(4-tpb)(NCBH3)2] (2·2-NapSMe and 2·H2O·3DMF, 4-tpb = 1,2,4,5-tetra(pyridin-4-yl)benzene, 2-NapSMe = 2-(methylthio)naphthalene) porous coordinatio...

Das Zusammenwirken von kernspingetriebener Relaxation und den Liganden in Lanthanoid-Einzelmolekülmagneten (SMMs) ist nicht vollständig geklärt. In ihrer Zuschrift (DOI: 10.1002/ange.202112764) berichten Liviu Ungur, Jun-Liang Liu und Mitarbeiter über zwei isotop-isomorphe HoIII-SMMs, deren Magnetisierungsdynamik den Wechsel der relativen Relaxatio...

Herein, we report the first example showing the reversible on-off switching of spin-crossover (SCO) property by solid state photochemical [2+2] reaction. The ultraviolet (UV) light-induced [2+2] cycloaddition reaction of 3-spy ligands in a two-dimensional (2D) Hofmann-type framework [Fe(3-spy)2{Pd(CN)4}] (1, 3-spy=3-styrylpyridine), which shows a h...

Nuclear‐spin driven relaxation collaborating with the ligands in lanthanide single molecule‐magnets (SMMs) remains ambiguous. In their Communication (DOI: 10.1002/anie.202112764), Liviu Ungur, Jun‐Liang Liu and co‐workers reported two HoIII isotopic–isomorphic SMMs, whose magnetization dynamics reveals the switch of the relative relaxation rates at...

Here we reported the deuteration of the metal-binding equatorial water molecules in a reported Ho III single-molecule magnet (SMM) with pentagonal-bipyramidal geometry, from [Ho(CyPh 2 PO) 2 (H 2 O) 5 ] 3+ to [Ho(CyPh 2 PO) 2 (D 2 O) 5 ] 3+ . The hyperfine structures originating from the nuclear spin of 165 Ho III can be clearly observed. Moreover,...

Spin crossover (SCO) compounds are bistable in nature but can exhibit five main types of SCO behaviors as collective phenomena. Here, incomplete, gradual, step, abrupt and hysteretic types of SCO behaviors can be observed in the magnetic curve of a 3D Hofmann-type metal-organic framework [Fe(dpt){Pt(CN)4}]·dpt·2.5H2O (1·dpt·2.5H2O, dpt = 2,5-di(pyr...

We report herein three air, thermal and solvent stable interlocked triacontanuclear giant nanocages, generated using a node and spacer concept. Interestingly, the crystal structures of the cages are not only nano-dimensional but also exist in the nano-dimension range, which was corroborated with microscopic images. The combination of microscopic an...

Here we reported the deuteration of the metal‐binding equatorial water molecules in a reported Ho III single‐molecule magnet (SMM) with pentagonal‐bipyramidal geometry, from [Ho(CyPh 2 PO) 2 (H 2 O) 5 ] 3+ to [Ho(CyPh 2 PO) 2 (D 2 O) 5 ] 3+ . The hyperfine structures originating from the nuclear spin of 165 Ho III can be clearly observed. Moreover,...

Stimuli‐responsive materials that can be reversibly switched by light are of immense interest. Among them, photo‐responsive spin crossover (SCO) complexes have great promises to combine the photoactive inputs with multifaceted outputs into switchable materials and devices. However, the reversible control the spin‐state change by photochromic guests...

Stimuli‐responsive materials that can be reversibly switched by light are of immense interest. Among them, photo‐responsive spin crossover (SCO) complexes have great promises to combine the photoactive inputs with multifaceted outputs into switchable materials and devices. However, the reversible control the spin‐state change by photochromic guests...

One-dimensional (1D) magnetic materials are intriguing due to their low densities, structural and chemical versatility. Herein a Dy(III) coordination polymer with significant single-molecule magnet behaviors has been constructed with strongly...

Spin-crossover (SCO) complexes with multiple spin states are promising candidates for high-order magnetic storage and multiple switches. Here, by employing the N,Nʹ-4-dipyridyloxalamide (dpo) ligand, we synthesize two Hofmann-type metal-organic frameworks (MOFs) [Fe(dpo){Ag(CN)2}2]•3DMF (1) and [Fe(dpo){Ag(CN)2}2]•0.5MeCN•2DEF (2), which exhibit gu...

A {Zn2Dy} single-ion magnet (SIM) with octahedral coordination geometry (Oh) was synthesized and characterized. The zero-field-cooled (ZFC) and field-cooled (FC) magnetic susceptibility measurement diverged below 4.1 K, revealing the presence of the magnetic blocking. Combining experimental data and ab initio calculations, we depicted the dynamic r...

We report here a linear fluoride-bridged Double-Decker Dysprosium metallacrown with high-performance SMM. The successful introduction of stronger magnetic exchange-coupling in the axial direction, which is collinear with the Ising-type magnetic anisotropy axis of dysprosium ions, plays a pivotal role in improving the SMM properties of the double-de...

Single-molecule magnets (SMMs) exhibiting open hysteresis loops may potentially apply to molecule-based information processing and storage. However, the capacity to retain magnetic memory is always limited by zero-field quantum tunneling of magnetization (QTM). Herein, a well-designed dysprosium metallacrown SMM, consisting of an endohedral approxi...

After changing the bridging ligand from π-conjugated to non-conjugated in didysprosium single-molecule magnets, the luminescence becomes enhanced and well-resolved, which helped us to investigate the magneto-optical correlation and the energy levels.

Two new two-dimensional (2D) coordination polymers, [FeII(L)2{PdII(SCN)4}] (L1 = 3-(9-anthracenyl)-pyridine (1) and L2 = 4-(9-anthracenyl)-pyridine (2)), were constructed by employing square-planar [Pd(SCN)4]2- building blocks. Compound 1 exhibits a complete spin-crossover (SCO) behaviour under normal atmospheric pressure, and represents the first...

In this contribution, we report the synthesis, characterization and luminescent-magnetic properties of Ln-clusters (Ln= Gd3+, Eu3+ and Tb3+) using a new pyridine-pyrazole functionalized ligand fitted with a chromophoric phenanthroline backbone. The unorthodox N-rich ligand forms isostructural trinuclear lanthanide complexes with a topology that clo...

Donor–acceptor Stenhouse adducts (DASAs) are a new class of negative photochromic molecules capable of linear‐to‐cyclic isomerization. We report three new DASAs that are responsive not only to visible‐light irradiation, but also to chemical stimuli including acidity and metal ions. The pendant pyridine group in the donor moiety has been found to pl...

Single-molecule magnets (SMMs) exhibit magnetization blocking in the presence of strong magnetic anisotropy. By employing molecular engineering, the blocking barrier can be significantly modified, remaining independent from other external factors, such as magnetic field. Taking advantage of hyperfine coupling of electronic and nuclear spins further...

Combining Ising‐type magnetic anisotropy with collinear magnetic interactions in single‐molecule magnets (SMMs) is a significant synthetic challenge. Herein we report a Dy[15‐MCCu‐5] (1‐Dy) SMM, where a DyIII ion is held in a central pseudo‐D5h pocket of a rigid and planar Cu5 metallacrown (MC). Linking two Dy[15‐MCCu‐5] units with a single hydroxi...

The magnetic hysteresis of a metallacrown magnet opens after introducing axial ferromagnetic by linking two mono‐decker Dy[15‐MCCu‐5] units with a single hydroxide bridge to give the double‐decker {Dy[15‐MCCu‐5]}2 single‐molecule magnet in which the anisotropy axes of the two DyIII ions are nearly collinear and the magnetic relaxation times are app...

Atropisomers refer to a subclass of chiral compounds that cannot be superposed with its mirror image. For a long time， chiral complexes play an important role in the fields of medicine， dyes， materials and natural products. Metal complexes as atropisomers have widespread applications in asymmetric catalysis. In contrast， fewer examples are known as...

By employing mixed ligands, a new trinuclear dysprosium complex [Dy3(dbm)3(L)4](ClO4)2·CH2Cl2·2MeOH (1, Hdbm = dibenzoylmethane; HL = 2-methoxy-6-((quinolin-8-ylimino)methyl)phenol) was synthesized by a one-pot reaction. According to structural characterization, all the 8-coordinated Dy(iii) sites are well arranged with slightly distorted square an...

Five new zinc coordination polymers based on flexible carboxylate ligands, namely, [Zn2(chtc)(H2O)]·3H2O (1), [Zn2(chtc)(4,4′-bpy)0.5] (2), [Zn(H2chtc)(bpe)] (3), [Zn(cis-chdc)(bpe)]·3H2O (4), and [Zn(trans-chdc)(bpe)(NO3)(H2O)]·H2O (5) (chtc/H2chtc = deprotonated/half-protonated cyclohexane-1e,2a,4a,5e-tetracarboxylic acid, cis/trans-chdc = cycloh...

Manipulating bistability at the molecular level, especially in single-molecule magnet (SMM) and spin-crossover (SCO) materials, has attracted enormous recent interest due to their multifaceted magnetic behaviour and potential applications in devices. Moreover, their fascinating properties can be further modulated via chemical modifications and exte...

We report herein synthesis, characterization and properties of some metal directed architectures using a new asymmetric, semi-rigid and bis-chelating pyridine-pyrazole based ligand, {N'-(amino (pyrimidin-2-yl)methylene)-3-(pyridin-2-yl)-1H-pyrazole-5-carbohydrazide (H2APPC)}. The H2APPC ligand forms multinuclear cage complexes with different transi...

We report a trinuclear dysprosium single-molecule magnet, [Dy3(μ3-CO3)(Clbbpen)3](CF3SO3)·6MeCN, which has a perfectly equilateral triangular structure. The Ising-like anisotropy of each Dy(III) site is oriented almost normal to the triangular plane, and magnetic dipole interactions between the spins cause an antiparallel Ising ground state. Crossi...

Single-molecule magnets (SMMs) are promising elements for quantum informatics. In the presence of strong magnetic anisotropy, they exhibit magnetization blocking - a magnetic memory effect at the level of a single molecule. Recent studies have shown that the SMM performance scales with the height of magnetization blocking barrier. By employing mole...

Controlling molecular magnetic anisotropy via structural engineering is delicate and fascinating, especially for single-molecule magnets (SMMs). Herein a family of dysprosium single-ion magnets (SIMs) sitting in pentagonal bipyramid geometry have been synthesized with the variable-size terminal ligands and counter anions, through which the subtle c...

Single-molecule magnets (SMMs), exhibiting magnetic bistability and slow magnetization relaxation, have fascinated scientific community for their promising applications in data storage and information processing. Great development has been achieved in lanthanide-based SMMs due to the unquenched orbital momentum and strong anisotropy of lanthanide i...

The first spin-crossover (SCO) complex with organic-inorganic hybrid perovskite strucuture (PPN)[Fe{Au(CN)2}3] (1) is reported, which displays three-step SCO behaviour. The light-induced excited spin-state trapping measurement gives T0 = 134 K...

Spin-crossover (SCO) materials with multiple spin states have received a special interest for their potential applications in multi-switches and high-order data storage. Herein, an unprecedented asymmetric seven-/eight-step SCO behavior is revealed in a three-dimensional Hofmann-type metal-organic framework [Fe(4-abpt){Au(CN)2}2]·2DMF·EtOH (4-abpt...

Among the responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here in a 2D Hofmann-type coordination polymer [Fe(isoq)2{Au(CN)2}2] (isoq = isoquinoline), a medium-temperature annealing process is introduced after a light/tem...

Single-molecule magnets (SMMs) with higher nuclearity provides opportunity for understanding the inherent nature of magnetic dynamics that are not limited to mononuclear SMMs. Herein, a centrosymmetric [Dy2(L)2(9-AC)4(MeOH)2]·2CH2Cl2·2H2O (1, where 9-AC = anthracene-9-carboxylate) and an equilateral triangular [Dy3(OH)(OMe)(L)3(dbm)3](OH)·3CH2Cl2·7...

Until now, the synthesis of a new multi-step spin-crossover (SCO) material is still a great challenge, although it has attracted for the potential applications in high order storage and multi-switches. Here, based on the four-step SCO complex Fe(dpoda){Ag(CN)2}2]•1.5naph (1•1.5naph, dpoda = 2,5-di-(pyridyl)-1,3,4-oxadiazole, naph = naphthalene), th...

p> Controlling molecular magnetic anisotropy via structural engineering is delicate and fascinating, especially for single-molecule magnets (SMMs). Herein a family of dysprosium single-ion magnets (SIMs) sitting in pentagonal bipyramid geometry have been synthesized with the variable-size terminal ligands and counter anions, through which the subtl...

The combination of magnetic interaction with high magnetic anisotropy provides a promising way for modulating/fine-tuning molecular magnetic behaviors. Here, we show the building block approach for the synthesis of a family of dilanthanide single-molecule magnets (SMMs) bridged with a cyanometallate starting from a monolanthanide SMM. Contingent on...

Among the responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here in a 2D Hofmann-type coordination polymer [Fe(isoq)₂{Au(CN)₂}₂] (isoq = isoquinoline), hidden multistability of the spin sta...

Reduction of the uranium(III) metallocene [(η 5 ‐C 5 i Pr 5 ) 2 UI] ( 1 ) with potassium graphite produces the 'second‐generation' uranocene [(η 5 ‐C 5 i Pr 5 ) 2 U] ( 2 ), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground‐state vale...

Reduction of the uranium(III) metallocene [(η5 -C5i Pr5 )2 UI] (1) with potassium graphite produces the "second-generation" uranocene [(η5 -C5i Pr5 )2 U] (2), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground-state valence electron c...

A zeolite-like gyroidal MOF (denoted as SCNU-1) constructed with Cu ions and 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol has a featured interpenetrating uninodal utc-c network which is for the first time found in the real structure. Moreover, SCNU-1 exhibits high thermal (>773 K), solvent, and acid/base stabilities; the largest CO2 affinity...

The dye molecule 1,2,4,5-tetra(4-pyridyl)benzene (bztpy), a tetradentate ligand, can be an excellent candidate to construct coordination polymers with photoluminescent properties. Here, based on Ag(I) and bztpy, three novel complexes that named [Ag2(bza)2(μ4-bztpy)] (1), [Ag2(μ-ipa)(μ4-bztpy)]•EtOH•3H2O (2) and [Ag3(pda)(μ-pda)1/2(μ4-bztpy)2]•3EtOH...

A new Hofmann-type metal-organic framework with bent pillar ligand, [Fe(dpoda){Ag(CN)2}2] (dpoda = 2,5-di-(pyridyl)-1,3,4-oxadiazole), was synthesized. Four-, two- and one-step spin-crossover (SCO) properties were obtained by using different sizes of aromatic...

The reactions of chiral ligand (R)/(S)-1,1'-binaphthyl-2,2'-diyl phosphate (R-HL/S-HL) and ErCl3·6H2O afford two pairs of di- and tetranuclear enantiomers [Er2(R/S-L)4(EtOH)6]Cl2·6.5EtOH (R-1, S-1) and [Er4(PO4)(R/S-L)8(EtOH)3(H2O)]2Cl(OH)·15EtOH·11H2O (R-2, S-2). The nuclearity of these complexes is controllable and depends on the reaction tempera...

Herein we report a stable and high performance Dy(III) single-ion magnet (SIM) showing an energy barrier of 944 K under zero dc field, with the open hysteresis up to 6...

Six new mononuclear FeII complexes of [FeL(NCE)2] family have been synthesized: L = N,N'-Dimethyl-N,N'-bis-(quinoline-2-ylmethyl)ethane-1,2-diamine (2MeLquinoline), E = S (1), Se (2), BH3 (3) and L = N,N'-Dibenzyl-bis-(pyridin-2-ylmethyl) ethane-1,2-diamine (DibenzylL), E = S (4a and 4b), Se (5), BH3 (6). Introduction of quinolyl groups in 1 − 3 re...