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In this work, we synthesized two Cu-based heterometal–oxo clusters 1and 2based on M(III)4O4(M = Fe/In) cubane centers and obtained the corresponding dimers 3and 4by connecting Cu atoms on the cluster cores with the auxiliary ligand 4,4′- bipyridine. They were characterized by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), and other tests. We conducted magnetic property study on compounds 1–4. The variable-temperature magnetic susceptibility test shows that compounds 1and 3exhibit significant ferromagnetic interactions at low temperatures, while compounds 2and 4exhibit overall antiferromagnetic interactions. When the metal at the cubane changes from magnetic Fe to nonmagnetic In, the magnetic interactions in the compound are weakened to a certain extent. Through dimerization, the extreme values of the variable-temperature magnetic susceptibility appear (1to 3)/disappear (2to 4) in the low-temperature section. We investigated the magnetic structure correlation of compounds 1–4through bond lengths, bond angles, and distances between magnetic atoms. The results showed that compounds 1–4exhibited significant magnetic coupling diversity.

Two copper(I)-sulfide clusters were synergistically modified by alkylthiols and conjugated N,S-heterocyclic ligands, i.e., Cu6(tBuS)2(MBIZ)4(designated as Cu6) and Cu8(tBuS)4(MBIZ)4·CH3OH·2H2O (designated as Cu8) (MBIZ = 2-mercaptobenzimidazole; tBuS = tert-butyl mercaptan). Introducing more thiol ligands led to further growth of the cluster core, resulting in the transformation from an octahedral to a di-tetrahedral configuration, accompanied by a slight increase in the Cu···Cu distance. Notably, both clusters demonstrate high chemical stability and superhydrophobicity as a result of the modification with surface ligands, being stable at least 1 week in a wide range of pH (1–14 for Cu6and 3–11 for Cu8). Moreover, Cu8exhibited near-infrared (NIR) photoluminescence (PL) emission and better third-order nonlinear optical (NLO) performance, with nonlinear absorption coefficients (β) of 3.5 × 10–10m/W, 3.5 times than that of Cu6and superior to the majority of crystalline chalcogenide semiconductors. Theoretical calculations indicate that the organic ligands and cluster core jointly optimize the electronic configuration in a manner that regulates the optical properties. This work provides a new perspective into understanding the relationship between cluster core/surface compositions and optical properties at an atomically precise level, which is instrumental in the accurate design and synthesis of stable and efficient third-order NLO materials.

One pseudopentasupertetrahedral chalcogenidometalate cluster, [(BuSn)3SnCd4S13(OH)]·6(H+DMP) (PPS-1; H+DMP = protonated 3,5-dimethylpiperidine), has been isolated by use of an organotin precursor. They are arranged to generate two types of tetrahedrally patterned cages, which further interconnect to form a diamond network. Owing to the covalent attachment of abundant alkyl groups, PPS-1 exhibits excellent hydrophobicity and could be used as an assembly substance for building liquid marbles.

Presented here are two titanium-based metal–organic frameworks (Ti-MOFs) based on well-defined [Ti6Cu6(μ3-O)2(μ2-O)9(HSO4)2(SO4)6], which can be easily obtained from a cheap Ti source and CuSO4and exhibited interesting magnetic properties. Furthermore, this clusters can be isolated in pure phase. Numerous uncoordinated sites of SO4and labile ligands on the Ti and Cu centers of this cluster make it a good candidate as a secondary building unit to construct various Ti-MOFs in the future.

Because of the high efficiency and mild reaction conditions, electrocatalytic CO2reduction (ECR) has attracted significant attention in recent years. However, the specific mechanism of the formation of the two-electron production (CO or HCOOH) in this reaction is still unclear. Herein, with density functional theory calculation and experimental manipulation, the specific mechanism of the selective two-electron reduction of CO2has been systematically investigated, employing the polyphenolate-substituted metalloporphyrinic frameworks, ZrPP-1-M (M = Fe, Co, Ni, Cu, and Zn), as model catalysts. Experimental observations and theoretical calculations discovered that ZrPP-1-Co is a more favorable catalyst for ECR among them. Compared with the formation of HCOOH, electroreduction of CO2into CO has more beneficial thermodynamic and kinetic routes with ZrPP-1-Co as a catalyst. After introducing the r-GO for improving the conductivity, the Faradaic efficiency for CO formation is 82.4% at −0.6 v (vs RHE).

Metal–organic frameworks (MOFs) are powerful toolkits to directly correlate structure–function relationships due to their well-defined structures. In this work, 5,15-di(3,4,5-trihydroxyphenyl)porphyrin (DTPP) and 5,10,15,20-tetra(3,4,5-trihydroxyphenyl)porphyrin (TTPP) are reacted with zirconium ions to afford two MOFs (Zr-DTPP and Zr-TTPP) with acid and base tolerance in the pH range of 1.0–14.0. Powder X-ray diffraction investigation combined with Rietveld refinement reveals the J-aggregated porphyrin building blocks confined by benzene-1,2,3-trisolate-zirconium chains in the newly prepared Zr-DTPP. Electron spin-resonance, singlet-oxygen determination, and sulfides oxidation experiments demonstrate a much better singlet-oxygen evolution of J-aggregated Zr-DTPP than that of unaggregated Zr-TTPP reported previously, in good contrast to the weaker photocatalytic capability disclosed for DTPP than that for TTPP in solution, consummating the theory of photosensitizer J-aggregation in boosting heterogeneous photoinduced singlet-oxygen generation.

The rational design of crystalline clusters with adjustable compositions and dimensions is highly sought after but quite challenging as it is important to understand their structural evolution processes and to systematically establish structure–property relationships. Herein, a family of organotin-based sulfidometalate supertetrahedral clusters has been prepared via mixed metal and organotin strategies at low temperatures (60–120 °C). By engineering the metal composition, we can effectively control the size of the clusters, which ranges from 8 to 35, accompanied by variable configurations: P1-[(RSn)4M4S13], T3-[(RSn)4In4M2S16] (R = nbutyl-Bu and phenyl-Ph; M = Cd, Zn, and Mn), T4-[(BuSn)4In13Cu3S31], truncated P2, viz. TP2-[(BuSn)6In10Cu6S31], and even T5-[(BuSn)4In22Zn6Cu3S52], all of which are the largest organometallic supertetrahedral clusters known to date. Of note, the arylstannane approach plays a critical role in regulating the peripheral ligands and further enriching geometric structures of the supertetrahedral clusters. This is demonstrated by the formation of tin-oxysulfide clusters, such as T3-[(RSn)4Sn6O4S16] (R = Bu, Ph, and benzyl = Be) and its variants, truncated T3, viz., TT3-[(BuSn)6Sn3O4S13] and augmented T3, viz., T3-[(Bu3SnS)4Sn6O4S16]. Especially, two extraordinary truncated clusters break the tetrahedral symmetry observed in typical supertetrahedral clusters, further substantiating the advantages offered by the arylstannane approach in expanding cluster chemistry. These organometallic supertetrahedral clusters are highly soluble and stable in common solvents. Additionally, they have tunable third-order nonlinear optical behaviors by controlling the size, heterometallic combination, organic modification, and intercluster interaction.

An isoreticular family of zirconium polyphenolate networks (ZrPP-n, n= 1 and 2), bridged by porphyrinic macrocycles in an eclipsed arrangement, have excellent stability toward water, especially strong basic media of saturated NaOH aqueous solution. Endowed with spatial alignment of protic sites, viz., partially protonated phenols of acidity enhanced by coordination to Zr4+, along with guest dimethylamine cations, the newly synthesized ZrPP-nreveal exceptional conductivity (8.0 × 10–3and 4.2 × 10–3S cm–1, for n= 1 and 2, respectively, pelleted sample, under 98% relative humidity at 25 °C).

Synergetic optical resolution and chiral amplification of tetrahedral Ti4L6cages by enantiopure coordination cations have been realized in this work. Anionic ΔΔΔΔ-[Ti4L6] and ΛΛΛΛ-[Ti4L6] cages (L = embonate) have been completely resolved by enantiopure Λ-[Mn(1R,2R-DCH)3] and Δ-[Mn(1S,2S-DCH)3] cations, respectively. Accordingly, two homochiral compounds (PTC-108(Δ)and PTC-108(Λ)) with three-dimensional supramolecular architectures were formed, containing larger diamondoid cages. Such an unusual resolution process clearly shows the stepwise transfer of homochirality from an enantiopure molecule to a resolved hydrogen-bonding aggregation and a final homochiral framework. Moreover, the separated homochiral Ti4L6cage presents enantioselective recognition toward chiral organic and pharmaceutical molecules. This work opens a novel resolution-dependent homochiral framework construction approach, and it also takes the homochiral tetrahedral Ti4L6cages with high solubility and stability into promising enantioselective application.

Rational design and regulation of atomically precise photocatalysts are essential for constructing efficient photocatalytic systems tunable at both the atomic and molecular levels. Herein, we propose a platform-based strategy capable of integrating both pore space partition (PSP) and open-metal sites (OMSs) as foundational features for constructing high-performance photocatalysts. We demonstrate the first structural prototype obtained from this strategy: pore-partitioned NiTCPE-pstp(TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene, pstp= partitioned stptopology). Nonpartitioned NiTCPE-stpis constructed from six-connected [Ni3(μ3–OH)(COO)6] trimer and TCPE linker to form 1D hexagonal channels with six coplanar OMSs directed at channel centers. After introducing triangular pore-partitioning ligands, half of the OMSs were retained, while the other half were used for PSP, leading to unprecedented microenvironment regulation of the pore structure. The resulting material integrates multiple advanced properties, including robustness, wider absorption range, enhanced electronic conductivity, and high CO2adsorption, all of which are highly desirable for photocatalytic applications. Remarkably, NiTCPE-pstpexhibits excellent CO2photoreduction activity with a high CO generation rate of 3353.6 μmol g–1h–1and nearly 100% selectivity. Theoretical and experimental studies show that the introduction of partitioning ligands not only optimizes the electronic structure to promote the separation and transfer of photogenerated carriers but also reduces the energy barrier for the formation of *COOH intermediates while promoting CO2activation and CO desorption. This work is believed to be the first example to integrate PSP strategies and OMSs within metal–organic framework (MOF) photocatalysts, which provides new insight as well as new structural prototype for the design and performance optimization of MOF-based photocatalysts.

Three novel heterometallic oxysulfide clusters with different coordination small organic molecules have been solvothermally synthesized and structurally characterized, i.e., [(nBuSn)3La(DTT)3(DETA)(L)] (nBuSn = n-butyltin; DTT = 1,4-dithiothreitol; DETA = diethylenetriamine; L = N,N-dimethylformamide (DMF) (1), N-methyl pyrrolidone (NMP) (2), and N-methyl formanilide (MFA) (3)). These clusters are a bowl-shaped structure, composed of a central DETA-coordinated La3+cation fixed in the triangle ring, [(nBuSn)3(DTT)3], and an amide molecule bonded to La3+confined inside the bowl. The coordinated amides can be changed and served as a molecular regulator to optimize the microsteric interaction between the clusters and further the physicochemical property. Remarkably, the crystals of 1exhibit strong blue-violet light emission with the photoluminescence quantum yield (PLQY) of 3.69%, which significantly exceeds than that of 2and 3and most of the other organotin oxysulfide clusters. Theoretical calculations and Hirshfeld surface analyses indicate that the weak amide-oriented intercluster interactions of the compounds can regulate their photoluminescence (PL) efficiency. This work provides a paradigm to reveal the relationships between its PL and structurally fine-tuned coordination species.

The title compound is hydrothermally synthesized from a mixture of KOH, Nb2O5, Si(OEt)4, and ZrOCl2in H2O (autoclave, 220 °C, 24 h, 70% yield).

Large orange‐red crystals of K11H [Sn4(SiW9O34)2] ·25H2O are synthesized by slow evaporation of an aq.