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A new noncentrosymmetric strontium borate, P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O (1), has been synthesized under the hydrothermal condition. The P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O shows a layered B−O network with 9‐ring windows in the ab plane. Sr2+ cations, H3BO3, and H2O molecules are located in the voids of layers and interlayers, respectively. The P1‐Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O is the first synthetic phase of veatchite, while the other three polymorphs are found in different natural minerals. This strontium borate is a potential deep‐ultraviolet‐transparent nonlinear‐optical (NLO) crystal whose second‐harmonic‐generation (SHG) intensity is 1.7 times that of KH2PO4 (KDP) and is phase‐matchable. The short wavelength cutoff edge of compound 1 is below 190 nm. Density functional theory (DFT) calculations show that the B−O units are responsible for the nonlinear optical property. [ABSTRACT FROM AUTHOR]

The syntheses of atomically precise silver (Ag) clusters stabilized by multidentate lacunary polyoxometalate (POM) ligands have been emerging as a promising but challenging research direction, the combination of redox‐active POM ligands and silver clusters will render them unexpected geometric structures and catalytic properties. Herein, we report the successful construction of two structurally‐new lacunary POM‐stabilized Ag clusters, TBA6H14Ag14(DPPB)4(CH3CN)9[Ag24(Si2W18O66)3] ⋅ 10CH3CN ⋅ 9H2O ({Ag24(Si2W18O66)3}, TBA=tetra‐n‐butylammonium, DPPB=1,4‐Bis(diphenylphosphino)butane) and TBA14H6Ag9Na2(H2O)9[Ag27(Si2W18O66)3] ⋅ 8CH3CN ⋅ 10H2O ({Ag27(Si2W18O66)3}), using a facile one‐pot solvothermal approach. Under otherwise identical synthetic conditions, the molecular structures of two POM‐stabilized Ag clusters could be readily tuned by the addition of different organic ligands. In both compounds, the central trefoil‐propeller‐shaped {Ag24}14+ and {Ag27}17+ clusters bearing 10 delocalized valence electrons are stabilized by three C‐shaped {Si2W18O66} units. The femtosecond/nanosecond transient absorption spectroscopy revealed the rapid charge transfer between {Ag24}14+ core and {Si2W18O66} ligands. Both compounds have been pioneeringly investigated as catalysts for photocatalytic CO2 reduction to HCOOH with a high selectivity. [ABSTRACT FROM AUTHOR]

Proteins UL31 and UL34 encoded by alphaherpesvirus are critical for viral primary envelopment and nuclear egress. We report here that pseudorabies virus (PRV), a useful model for research on herpesvirus pathogenesis, uses N‐myc downstream regulated 1 (NDRG1) to assist the nuclear import of UL31 and UL34. PRV promoted NDRG1 expression through DNA damage‐induced P53 activation, which was beneficial to viral proliferation. PRV induced the nuclear translocation of NDRG1, and its deficiency resulted in the cytosolic retention of UL31 and UL34. Therefore, NDRG1 assisted the nuclear import of UL31 and UL34. Furthermore, in the absence of the nuclear localization signal (NLS), UL31 could still translocate to the nucleus, and NDRG1 lacked an NLS, thus suggesting the existence of other mediators for the nuclear import of UL31 and UL34. We demonstrated that heat shock cognate protein 70 (HSC70) was the key factor in this process. UL31 and UL34 interacted with the N‐terminal domain of NDRG1 and the C‐terminal domain of NDRG1 bound to HSC70. Replenishment of HSC70ΔNLS in HSC70‐knockdown cells, or interference in importin α expression, abolished the nuclear translocation of UL31, UL34, and NDRG1. These results indicated that NDRG1 employs HSC70 to facilitate viral proliferation in the nuclear import of PRV UL31 and UL34. [ABSTRACT FROM AUTHOR]

The stable Zr6‐based coordination framework Ru‐1 was assembled via the linkage of Zr6‐organic layers and photosensitized Ru(N^N)3‐metalloligand. Based on its 1D open channel and the incorporation of Ru(N^N)3‐photosensitizer, it can serve as a highly efficient heterogeneous catalyst in the aerobic photooxidation reactions, including photooxidation of sulfides, coupling of amines and oxidative hydroxylation of arylboronic acids. The stability and catalytic performance of recycled Ru‐1 was also explored. [ABSTRACT FROM AUTHOR]

A new acentric borate, K2Na3[{B6O10(OH)}‐{B3O4(OH)3}] ⋅ H2O (1) has been made under solvothermal condition. 1 has layered structure made by B6O13(OH)‐based chains and B3O5(OH)3‐bridging clusters. Second‐harmonic generation (SHG) measurements reveal that 1 is a phase‐matchable nonlinear optical (NLO) material, showing the SHG signal intensity of 1.8 times that of KDP (KH2PO4). Besides, UV‐Vis diffuse reflectance spectrum shows that 1 has the short deep UV (DUV) absorption cutoff edge of 198 nm. Thermogravimetric analysis reveals it has good thermal stability. Also 1 represents firstly mixed oxoboron clusters‐made 2D layered borate with NLO property. [ABSTRACT FROM AUTHOR]

Three isostructural lanthanide metal‐organic frameworks (Ln‐MOFs) were synthesized with uncoordinated N^N site, and the Ru(N^N)3 photosensitizer was introduced via coordination link. These functionalized frameworks showed excellent performance in the photocatalytic oxidation of sulfides with good conversion and high sulfoxide selectivity. [ABSTRACT FROM AUTHOR]

A new hexa‐TiIV‐substituted sandwich‐type silicotungstate, Na2(H2enMe)4[Ti6(µ‐O)9(A‐α‐SiW9O34H2)2]·16H2O (1, enMe = 1,2‐diaminopropane) has been synthesized under mild hydrothermal conditions and characterized by FT‐IR spectroscopy, elemental analysis, thermogravimetric analysis, single‐crystal and powder X‐ray diffraction. Compound 1 contains a dimeric polyoxoanion with two [A‐α‐SiW9O34]10– Keggin moieties sandwiching a trigonal‐prismatic [Ti6(µ‐O9)]6+ cluster. The catalytic performance of 1 was evaluated for the oxidative decontamination of chemical warfare agent, i.e. sulfur mustard simulant, 2‐chloroethyl ethyl sulfide (CEES), using H2O2 under ambient conditions, showing that 1 is an excellent catalyst for the rapid and complete transformation from CEES to nontoxic 2‐chloroethyl ethyl sulfoxide (CEESO) with 100 % selectivity. In addition, 1 exhibits good stability and recyclability. [ABSTRACT FROM AUTHOR]

Under hydrothermal conditions, two families of new CuII‐substituted sandwich‐type germanotungstates (GTs): Cu6‐GTs (enH2)2[Cu(en)2]2[Cu6(en)2(H2O)2(B‐α‐GeW9O34)2]⋅4H2O (1), H4[Cu(deta)(H2O)]2[Cu6(en)2(H2O)2(B‐GeW9O34)2]⋅8H2O (2), [Cu(en)(H2O)2]2[Cu(en)2]2[Cu6(en)2(H2O)2(B‐α‐GeW9O34)2]⋅8H2O (3) (en=ethylenediamine, deta=diethylenetriamine) and Cu4‐GTs H4[Cu(H2O)4]2[Cu(H2O)5]2[Cu4(H2O)2(B‐α‐GeW9O34)2]⋅8H2O (4), H10[Cu(H2O)3(Cl)]2[Cu4(B‐α‐GeW9O34)2]⋅8H2O (5), H8[Na(H2O)4]2[Cu(H2O)3(Cl)]2[Cu4(B‐α‐GeW9O34)2]⋅8H2O (6) have been made and characterized. Single‐crystal structural analyses indicate that 1–3 contain a belt‐like hexa‐CuII substituted sandwich‐type [Cu6(en)2(H2O)2(B‐α‐GeW9O34)2]8+ unit. Notably, 1–3 are rare organic‐inorganic hybrid polyoxometalates with [Cu6(en)2(H2O)2(B‐α‐GeW9O34)2]8− subunits, displaying the assembly from 1‐D chain to 3‐D framework by the [Cu(en)2]2+ or [Cu(deta)2(H2O)]2+ linkers. 4–6 contain rhomb‐like tetra‐CuII substituted sandwich‐type [Cu4(H2O)n(B‐α‐GeW9O34)2]12− (n=2, 0) units linked by [Cu(H2O)4]2+ or [Cu2(H2O)6Cl2]+ clusters to from 1‐D chain. Magnetic measurements performed on 3 indicate the occurrence of ferromagnetic interactions within the copper ions. Furthermore, the electrochemical and electro‐catalysis properties of 3 have been studied in 0.02 M H2SO4 + 0.5 M Na2SO4 solution, and show good electro‐catalytic activity to the reduction of nitrite. [ABSTRACT FROM AUTHOR]

A new trinuclear Zr4+ cluster substituted decanuclear hetero‐metal sandwich tungstoantimonate aggregate [H2N(CH3)2]7Na3H5{[Zr3(OAc)W7(H2O)O25][B‐α‐SbW9O33]2}·22H2O (1) has been synthesized under hydrothermal condition by reacting [B‐α‐SbW9O33]9– precursor, ZrOCl2·8H2O, Na2WO4·2H2O and dimethylamine hydrochloride in sodium acetate buffer (pH = 4.8) and structurally characterized by elemental analyses, IR spectrum, thermogravimetric analysis (TGA), powder X‐ray diffraction (PXRD) and single‐crystal X‐ray diffraction. The structure unit of 1 consists of a new sandwich tungstoantimonate (TA) unit {[Zr3(OAc)W7(H2O)O25][B‐α‐SbW9O33]2}15– constituted by two trivacant Keggin [B‐α‐SbW9O33]9– fragments linked through an unseen hetero‐metal cluster [Zr3(OAc)W7(H2O)O25]3+. In addition, the polyoxoanion can also be described as two trivacant Keggin [B‐α‐SbW9O33]9– fragments and one divacant Lindqvist [W4O16]8– linked by a hexanuclear hetero‐metal cluster [Zr3(OAc)W3(H2O)O9]11+ link. Moreover, the solid‐state electrochemistry and electrocatalytic performances of 1 have been measured in 0.5 mol L–1 Na2SO4 + H2SO4 aqueous solution, and the results show that 1 illustrates comparatively apparent catalytic activities toward the BrO3– and H2O2 reduction. A new trinuclear Zr4+ cluster substituted decanuclear hetero‐metal sandwich tungstoantimonate has been made and characterized, also its electrocatalytic properties have been investigated. [ABSTRACT FROM AUTHOR]

A previously unknown inorganic–organic hybrid polyoxidometalate constructed from oxalate‐functionalized tetra‐ZrIV‐substituted dimeric silicotungstate, (NH4)3Na5K6[Zr4(µ3‐O)2(µ‐OH)2(ox)2(SiW10O37)2]·23H2O (1, ox = oxalate) has been synthesized under mild hydrothermal conditions and characterized by FTIR spectroscopy, elemental analysis, thermogravimetric analysis, single‐crystal and powder X‐ray diffraction. Compound 1 contains a centrosymmetric polyoxidoanion structure with two [SiW10O37]10– units sandwiching a [Zr4(µ3‐O)2(µ‐OH)2(ox)2]6+ cluster. The catalytic performances of 1 involving oxygenation reactions of thioethers by H2O2 were evaluated, showing that 1 is an excellent catalyst for the catalytic oxidation of thioethers to sulfoxides/sulfones. A new tetra‐ZrIV‐substituted dimeric silicotungstate with two [SiW10O37]10– units sandwiched by an oxalate‐functionalized Zr4 cluster was made and characterized. This was used as a catalyst for catalyzing the oxidation of various thioethers with H2O2, showing excellent catalytic performance. [ABSTRACT FROM AUTHOR]

Abstract: In the presence of the larger [H2N(CH3)2]+ and K+ counter cations as structure‐stabilizing agents, a class of unprecedented selenium and lanthanide (Ln) simultaneously bridging tetra‐vacant Dawson‐like selenotungstate aggregates [H2N(CH3)2]2Na9K2H19{[Ln4W4 Se4O22(H2O)5](Se2W14O52)2}2⋅60 H2O [Ln=TbIII (1), DyIII (2), HoIII (3), ErIII (4), TmIII (5), YbIII (6)] have been obtained by the one‐pot assembly reaction of Na2WO4⋅2 H2O, Ln(NO3)3⋅6 H2O, and Na2SeO3 under moderately acidic aqueous conditions and the complexes were structurally characterized by elemental analyses, IR spectra, single‐crystal X‐ray diffraction, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. It should be noted that the appropriate molar ratio of Se/W is extremely important in the formation of 1–6 and can effectively ameliorate the yield of 1–6. Moreover, dimethylamine hydrochloride is also indispensable and plays a considerably important role in improving the solubility of Ln ions and stabilizing the structures of 1–6. The main polyoxoanion skeletons of 1–6 are constructed from two sandwich‐type tetra‐vacant Dawson‐like {[Ln4W4Se4O22(H2O)5](Se2W14O52)2}16− half‐units linked through two W‐O‐Ln bridges. The sandwich‐type half‐unit comprises two tetra‐vacant Dawson‐like [Se2W14O52]12− fragments encapsulating a unique dodecanuclear Se‐Ln‐W [Ln4W4Se4O22(H2O)5]8+ oxo cluster. Their solid‐state visible and NIR fluorescent properties and lifetime decay behaviors were measured and their solid‐state luminescent spectra mainly demonstrate the characteristic emission bands of Ln3+ ions. Moreover, the dominant wavelengths, the color purity, and correlated color temperatures of 1–5 have been also calculated. In addition, the luminous flux values of 1–5 are 2031, 6992, 3071, 921, and 477 lumen, respectively. [ABSTRACT FROM AUTHOR]

Abstract: The grafts of fluorophores 9‐anthraldehyde (AD) and 9‐phenanthrenecarboxaldehyde (PD), respectively, on the one‐dimensional spin‐crossover compound [Fe(L)3](ClO4)2 (FeL, L=4‐amino‐1,2,4‐triazole) by post‐synthetic aldimine condensation reactions produced two spin‐crossover (SCO)–fluorescent hybrid materials, that is, FeL‐AD and FeL‐PD. The spin‐crossover critical temperatures of the two materials both centered at Tc↓=254 and Tc↑=256 K, whereas the fluorescence intensities of the two materials featured functions of the temperature that strictly synchronized with the spin‐crossover processes, which showed that the ligand‐centered fluorescence was dominated by the spin states of the ferrous ions. The bifunctional entities (spin‐crossover centers and fluorophores) in FeL‐AD or FeL‐PD showed spectral band overlap that purported the Förster resonance energy transfer mechanism of such spin‐crossover–fluorescence correlation. The post‐synthetic modification of SCO materials and the relationship between the fluorescence and the SCO may be helpful in the development of multifunctional materials that can be sensitive to multiple stimuli. [ABSTRACT FROM AUTHOR]

The cooperative effect of inorganic and organic cotemplates led to two layered borates: centrosymmetric (CS) Na2(H2en)[B5O8(OH)]2[B3O4(OH)]2 (1; en = ethylenediamine) and noncentrosymmetric (NCS) Na3(HCOO)[B5O8(OH)] (2). Compound 1 features coupled layers extended by two different oxoboron clusters, which are rare in borates. The Na+ cations are located in the channel and hold the coupled layers in tight inorganic B-O-Na layers, while H2en2+ cations reside in channels between inorganic layers. Compound 2 is the first NCS borate directed by inorganic and organic species simultane-ously and features acentric [B5O8(OH)]n 2n- layers. It exhibits a good second harmonic generation efficiency of about 1.9 times that of potassium dihydrogenphosphate and is phasematchable, and the UV cutoff edge below 200 nm makes 2 a potential UV nonlinear optical material. Investigation of the fluorescence properties indicated that the new borates are potential blue fluorescent materials. In addition, structure elucidation revealed that host-guest symmetry matching plays a key role in the formation of CS 1 and NCS 2. [ABSTRACT FROM AUTHOR]

A trizirconium(IV)-substituted sandwich-type polyoxotungstate, K7.5H6.5[Zr3(µ2-OH)2(µ2-O)(A-α-GeW9O34)(1,4,9-α-P2W15O56)] ·16.5H2O ( 1), was hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and single-crystal X-ray diffraction. The structural unit of 1 consists of trilacunary Dawson-type phosphotungstate and trilacunary Keggin-type germanotungstate units that are linked by a trizirconium(IV) cluster. [ABSTRACT FROM AUTHOR]

Two novel alkali/alkaline-earth borates, Ba6[B6O9(OH)6]2(H3BO3) ( 1) and Li7MAlB12O24 (M=Ba, Sr, Ca) ( 2 a- c), with 1D and 3D structures have been made hydrothermally and characterized. 1 features a rare 1D anionic chain built by hexaborate clusters of B6O11(OH)6; each made of six BO4/BO2(OH)2 tetrahedra. The anionic chains are embedded in the channels of a Ba6-based wheel-cluster open-framework. On the basis of the structural analyses of 1, by incorporating Al atoms as the linkers and tuning the reaction conditions, the novel anhydrous 3D aluminoborates (ABOs) 2 a- c have been successfully obtained, constructed from B6O14-based cluster chains and AlO6 octahedra. The 3D ABO framework and 3D Ba-O-Li network are interpenetrated to give a final dense structure. The study not only realized the expansion of the structure from the 1D chain of 1 to the 3D dense ABOs 2 a- c, but also obtained the first 3D AlO6-containing ABOs made under hydrothermal conditions. Different from the previously known 4-connected zeolite-type ABOs, alternately arranged from AlO4 tetrahedra and oxo-boron clusters, the AlO6 octahedra in 2 a- c as the linkers join to six 1D B6O14-based cluster chains to produce 3D ABOs. The optical diffuse reflectance spectra reveal that 2 a- c have wide range transparency. In addition, the thermal property analysis proves that 2 a- c are congruently melting compounds and possess high thermostability. [ABSTRACT FROM AUTHOR]

Two new copper borates, namely H6[(μ4-O)Cu4@B20O32(OH)8]⋅25 H2O ( 1) and H6[(μ4-O)Cu4@B20O32(OH)8]⋅34 H2O⋅8 H3BO3 ( 2), with 3D supramolecular framework have been made under solvothermal conditions, which built by novel cubic supramolecular cages with mesoscale cavities via the H-bondings. Interestingly, the cage is assembled by [(μ4-O)Cu4@B20O32(OH)8] ({Cu4@B20}) cluster units with different point-group symmetry. Owing to extra H3BO3 molecules participated in building the supramolecular framework, 2 has a larger cubic cage size and higher non-framework volume, leading to the cage size extended to mesoporous size set as a version of '' 1 plus'. [ABSTRACT FROM AUTHOR]

Three types of serine-decorated rare- earth-containing arsenotungstate [H2N(CH3)2]6NaH[RE2 W4O10(H2O)8(Ser)2(B-α-AsW9O33)2]⋅30 H2O (RE3+=Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, and Y3+; 1), [H2N(CH3)2]6Na6− xRE xH4−2 x[RE4W8O19(H2O)10+ y(OH)2(Ser)2(B-α-AsW9O33)4]⋅ n H2O (RE3+=Tb3+, x=1, y=2, n=36; RE3+=Dy3+, Ho3+, Er3+, Yb3+, Y3+, x=0, y=0, n=38; RE3+= Tm3+, x=1, y=0, n=38; Ser=serine; 2), and [H2N(CH3)2]6−2 xNa2+3 xRE xH10−6 x+ y[RE4W8O19(H2O)8(OH)2(Ser)4(B-α-AsW9O33)4]⋅Cl y⋅ n H2O (RE3+=Ce3+, Pr3+, x=1, y=0, n=65; RE3+=Nd3+, Sm3+, x=0, y=0, n=65; RE3+=Eu3+, Gd3+, x=1, y=2, n=45; 3) were synthesized with the participation of the organic solubilizers dimethylamine hydrochloride and l-serine and were structurally characterized. The use of different amounts of rare-earth salts results in the structural transformation from dimerization to tetramerization of types 1- 3. Type 1 is a dimeric sandwich-type assembly of a dual-Ser-participating [RE2W4O10(H2O)8(Ser)2]10+ entity sandwiched by two [B-α-AsW9O33]9− moieties, whereas types 2 and 3 have a tetrameric square structure formed by four [B-α-AsW9O33]9− moieties that anchor a dual/tetra- Ser-participating [RE4W8O19(H2O)10+ y(OH)2(Ser)2]20+ or [RE4W8O19(H2O)8(OH)2(Ser)4]20+ core. The solid-state luminescence properties and lifetime-decay behaviors of these compounds were investigated. The chromaticity coordinates, dominant wavelengths, color purities, and correlated color temperatures were also calculated. [ABSTRACT FROM AUTHOR]

Under hydrothermal conditions, replacement of the water molecules in the [MnIII4MnII2O4(H2O)4]8+ cluster of mixed-valent Mn6 sandwiched silicotungstate [(B-α-SiW9O34)2MnIII4MnII2O4(H2O)4]12− ( 1 a) with organic N ligands led to the isolation of five organic-inorganic hybrid, Mn6-substituted polyoxometalates (POMs) 2- 6. They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse-reflectance spectroscopy, and powder and single-crystal X-ray diffraction. Compounds 2- 6 represent the first series of mixed-valent {MnIII4MnII2O4(H2O)4− n(L) n} sandwiched POMs covalently functionalized by organic ligands. The preparation of 1- 6 not only indicates that the double-cubane {MnIII4MnII2O4(H2O)4− n(L) n} clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [MnIII4MnII2O4(H2O)4]8+ cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed-valent POMs substituted with transition-metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single-molecule magnet behavior. [ABSTRACT FROM AUTHOR]

Through adjustment of the pH value of the reaction system, two series of 3 D lanthanide(III)-copper(I) coordination polymers, namely [Ln2(na)7Cu6Br5(H2O)2] [Ln=La ( 1), Ce ( 2), Pr ( 3), Nd ( 4), Sm ( 5), Eu ( 6), Gd ( 7), Tb ( 8)] and [La2(na)7Cu3Br2(H2O)2]⋅H2O ( 9) (na−=nicotinate), are synthesized hydrothermally and characterized fully. It is worth nothing that these two series of heterometallic compounds are constructed from similar ladder-like Ln-organic chains, but different copper(I) halide clusters. The luminescence properties of the compounds with Nd ( 4), Eu ( 6), and Tb ( 8) are also investigated. [ABSTRACT FROM AUTHOR]

A new borate LiBa3(OH)[B9O16][B(OH)4], which combines the uniform porosity of open-frameworks with the extraordinary NLO properties of borates, has been obtained under hydrothermal conditions by using mixed lithium and barium ions as templates. The framework displays an acs-type net with large 21-ring channels. The second harmonic generation (SHG) measurement shows that it is a type I phase-matchable material with a strong SHG signal intensity about 3.1 times that of KDP (KH2PO4). UV/Vis-NIR diffuse reflectance analysis indicates that the compound has a wide transparency range with the short-wavelength absorption edge below 200 nm. These characteristics reveal that the compound is a promising deep-UV nonlinear optical material. [ABSTRACT FROM AUTHOR]

A new approach to prepare heterometallic cluster organic frameworks has been developed. The method was employed to link Anderson-type polyoxometalate (POM) clusters and transition-metal clusters by using a designed rigid tris(alkoxo) ligand containing a pyridyl group to form a three-fold interpenetrated anionic diamondoid structure and a 2D anionic layer, respectively. This technique facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework. [ABSTRACT FROM AUTHOR]

Compared with metal organic frameworks (MOFs), the proton conductivity of cluster organic frameworks has been less studied. Herein, two supertetrahedral cluster organic frameworks (SCOFs) have been made that show two-fold interpenetrated networks built by trivalent lanthanide tetrahedral clusters and monovalent cuprous T3-supertetrahedral clusters. The structure analysis, second harmonic generation signals, and solid-state circular dichroism spectroscopy consistently reveal the chirality of these SCOFs. Remarkably, the water-stable SCOFs show a high proton conductivity value of 1.4×10−3 S cm−1 at 80 °C and 95 % RH (relative humidity). [ABSTRACT FROM AUTHOR]

Two sandwiched cluster organic frameworks, Eu6(OH)2Cu9I6L12(ox)3 ⋅H2O ⋅ClO4 ( FJ-23, HL=4-pyridin- 4-yl-benzonic acid, ox=oxalate) and Eu6Cu7I7L12(OAc)6(H2O)2 ⋅2 H2O ( FJ-24, OAc=acetate) with bnn hexagonal BN topologies have been successfully made; these frameworks were assembled by nanosized graphene-like lanthanide wheel clusters and nanoscale trigonal prism metalloligands. The cooperation of small equatorial ligands and axially trigonal prism metalloligands plays a key role in the construction of such 5-connected nets. Furthermore, the thermal stabilities and chiral characteristics were also studied. [ABSTRACT FROM AUTHOR]

A series of open-framework aluminoborates (ABOs), namely, [Zn2(en)5][Al2B10O20] ( 1), [Zn(en)(dien)][AlB5O10] ( 2), [Zn(en)3][AlB7O12 (OH)2] ( 3), [Zn(en)2][AlB5O10] ( 4), K7{AlO0.5[BO2(OH)]Zn@[B12O21(OH)3]}⋅H2O ( 5) (en=ethylenediamine, dien=diethylenetriamine) have been made under mild solvothermal conditions and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR and UV/Vis spectroscopy, thermogravimetric analysis, and nonlinear optical determination. They were classified as two types: Compounds 1- 4 contain intersecting channels and exhibit various 4-connected nets built by AlO4 tetrahedra and oxo boron clusters, zinc-amine complexes act as the templates ( 1- 3) or directly bond to the walls of the ABO ( 4); compound 5 exhibits a double-layer structure made by nanosized [BO2(OH)]Zn@[B12O21(OH)3] ({BZn@B12}) clusters with Al2O7 dimers, the channels are within the layer. The second harmonic generation (SHG) measurement shows that the SHG responses of 1- 3 are about 2.5, 1.6, and 0.5 times that of KH2PO4. Compounds 1- 2 are type I phase-matchable materials. UV/Vis spectroscopy indicates that compounds 1- 5 are wide-band-gap semiconductors. [ABSTRACT FROM AUTHOR]

A novel 3-connected SrSi2-type 3D chiral framework constructed from hexa-NiII-cluster-substituted polyoxometalate (POM) units [Ni(enMe)2]3[WO4]3[Ni6(enMe)3(OH)3PW9O34]2⋅9H2O ( 1) (enMe=1,2-diaminopropane) has been made from a hydrothermal synthetic method. This POM represents the first 3D framework based on {Ni6PW9} units and {WO4} connectors. [ABSTRACT FROM AUTHOR]

Three novel hexa-Ni-substituted Dawson phosphortungstates [Ni6(en)3(H2O)6(μ3-OH)3(H3P2W15O56)] ⋅14 H2O ( 1), [Ni(enMe)2(H2O)][Ni6(enMe)3(μ3-OH)3(H2O)6(HP2W15O56)] ⋅ 10 H2O ( 2), and [Ni(enMe)2]3[Ni(enMe)2(H2O)][Ni(enMe)(H2O)2][Ni6(enMe)3(μ3-OH)3(Ac)2(H2O)(P2W15O56)]2 ⋅6 H2O ( 3) (en=ethylenediamine, enMe=1, 2-diaminopropane, Ac=CH3COO−) have been made under hydrothermal conditions and were characterized by IR spectroscopy, elemental analysis, diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The common structural features of compounds 1- 3 contain the similar hexa-Ni-substituted Dawson polyoxometalate (POM) units that can be viewed as a [Ni6(μ3-OH)3]9+ cluster capping on a [P2W15O56]12− fragment. Compounds 1 and 2 are two isolated clusters, whereas compound 3 is the first 3D POM framework constructed from hexa-Ni-substituted Dawson POM units and Ni(enMe) complex bridges. The preparations of compounds 1- 3 not only indicate that triangle coplanar Ni6 clusters are very stable fragments in both trivacant Keggin and trivacant Dawson POM systems, but also offer that the hydrothermal technique can act as an effective strategy for making novel Dawson-type high-nuclear transition-metal cluster substituted POMs by combination of lacunary Dawson precusors with transition-metal cations in the tunable role of organic ligands. In addition, magnetic measurements illustrate that there exist overall ferromagnetic interactions in compound 3. [ABSTRACT FROM AUTHOR]

Two new cluster open framework borates, NaB3O5·0.5H2O (1) and NH4NaB6O10 (2) have been made under solvothermal conditions and characterized by IR, emission, and diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. The common structural features contain the oxoboron cluster building units, B3O7 and B6O13 cluster units for 1 and 2, in which the B3O7 and B6O13 clusters act as 4- and 6-connected nodes to further link each other, resulting in chiral qtz and achiral pcu nets, respectively. [ABSTRACT FROM AUTHOR]

A new inorganic-organic hybrid solid, [Zn(dap)2][AlB5O10], combining the structural features of 3D open-framework inorganic solids and 2D metal-organic coordination polymers has been synthesized under solvothermal conditions. The compound displays extensive luminescence and moderate second-harmonic-generation efficiency. [ABSTRACT FROM AUTHOR]

Two series of sandwich frameworks, [La6(μ3-OH)2(ox)3L12Cu11(μ3-X)6(μ2-X)3]⋅8 H2O (X=Br/Cl, FJ-21 a/b; L=4-pyridin-4-yl-benzonate; ox=oxalate) and [Ln4(OAc)3(H2O)4L9][Cu(μ3-I)]@[Cu10(μ3-I)(μ4-I)6(μ5-I)3]⋅7H2O (Ln=Pr/Nd/ Sm/Eu, FJ-22 a/ b/ c/ d; OAc=acetate) have been hydrothermally prepared. These sandwich frameworks are assembled by two different kinds of nanosized lanthanide(III) and copper(I) wheel cluster units, La18 and 3Cu@Cu24 in FJ-21, Ln24 and Cu2@Cu24 in FJ-22. The synergistic coordination between organic ligands, L and oxalate/acetate, leads to the formation of La18 and Ln24 wheels, while the synergistic coordination between organic L and inorganic Br/I ligands results in 3Cu@Cu24 and Cu2@Cu24 wheels for FJ-21 and FJ-22, respectively. Thus, two types of synergistic coordination between two different organic ligands, as well as inorganic and organic ligands are simultaneously observed in FJ-21 and FJ-22. [ABSTRACT FROM AUTHOR]

Two unique organic-inorganic hybrid polyoxometalates constructed from Preyssler-type [Na(H2O)P5W30O110]14− ({P5W30}) subunits and TM/Ln-carboxylate-Ln connectors (TM=transition metal, Ln=lanthanide), KNa7[{Sm6Mn(μ-H2O)2(OCH2COO)7(H2O)18}{Na(H2O)P5W30O110}] ⋅22 H2O ( 1) and K4[{Sm4Cu2(gly)2(ox)(H2O)24}{NaP5W30O110}]Cl2 ⋅25 H2O ( 2; gly=glycine, ox=oxalate) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV/Vis-NIR spectra, thermogravimetric analyses, power X-ray diffraction, and single-crystal X-ray diffraction. Compound 1 displays one interesting 3D framework built by three types of subunits, {P5W30}, [Sm2Mn(μ-H2O)2(OCH2COO)2(H2O)5]4+, and [Sm4(OCH2COO)5 (H2O)13]2+, whereas 2 also manifests the other intriguing 3D architecture created by three types of subunits, {P5W30}, [SmCu(gly)(H2O)8]4+, and [Sm2(ox)(H2O)8]4+. To our knowledge, 1 and 2 are the first 3D frameworks that contain {P5W30} units and TM/Ln-carboxylate-Ln connectors. The fluorescent properties of 1 and 2 have been investigated. [ABSTRACT FROM AUTHOR]

Two acentric metal borates Ba3M2‐ [B3O6(OH)]2[B4O7(OH)2] (M=Al, Ga) have been made under hydrothermal conditions; the MO4 groups and two types of oxoboron cluster units interconnect to form a 3D porous layer with 9‐/14‐membered‐ring intersecting channels (see figure), showing a good second harmonic generation effect of about three times that of KH2PO4 (KDP). [ABSTRACT FROM AUTHOR]

A polyoxometalate (POM) based on the assembly of [P5W30O110]15- ({P5W30}) units and copper ions, {(H5P5W30O110)2[(en)4Cu4(μ3-OH)3(μ-H2O)]2}[Cu(en)2]4[Cu(H2O)3] ·12H2O (en = ethylenediamine) ( 1), has been made under hydrothermal conditions and characterized by single-crystal X-ray diffraction (XRD), elemental analysis, IR spectroscopy, thermogravimetric analysis, and power XRD; saturated {P5W30} was used as the precursor to make the new POM. POM 1 is the first 3D {P5W30}-based POM linked by late transition metal copper complex ions, and it also features the rarely seen linkages of the saturated {P5W30} units and [Cu4(μ3-OH)3(μ-H2O)] ({Cu4}) clusters. In the structure of 1, the {P5W30} units and {Cu4} clusters are alternately linked to form dimeric units and are further connected by two kinds of [Cu(en)2]2+ complex bridges, which results in the 3D framework. [ABSTRACT FROM AUTHOR]

Two types of new polyoxometalates (POMs) based on circular P8W48 clusters with different tetralanthanide (Ln) clusters and octamanganese centers, [K(H2O)2]4[K4(μ-H2O)4(H2O)4]2{[Ln2(μ-OH)4(H2O) x]2(H24P8W48O184)} · yH2O [Ln = Nd ( 1), Sm ( 2), Tb ( 3)] and [K(H2O)2]4[K4(μ-H2O)8]2[K(H2O)]8{[Mn8(H2O)16](H4P8W48O184)} ·36H2O ( 4) have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetry (TG), and powder XRD. Compounds 1- 3 are the first series of Ln-containing P8W48-based POMs that use P2W12O4814- as the precursor; previously known P8W48-based POMs used P8W48O18440- as the precursor. In 4, eight manganese ions were incorporated. Owing to the different radii of the Ln and Mn ions, the four large Ln ions are divided into two {Ln2} clusters located on two sides of the cavity of the P8W48 wheel in 1- 3, but the eight small manganese ions in 4 only bond to the inside of the P8W48 wheel and do not form manganese clusters. The magnetic properties of 3 are discussed. [ABSTRACT FROM AUTHOR]

The title compound, {(C12H13N2)2[Mo5O16]}n, was synthesized under hydrothermal conditions. The structure contains a twodimensional layer, constructed from [(Mo4O14)n]4n- chains linked through MoO6 octahedra, which lie across twofold axes. The [(Mo4O14)n]4n- chain consists of [Mo4O14]4- clusters connected to one another by sharing their MoO5 squarepyramidal and MoO6 octahedral vertices in an anti disposition. The layers are linked by the cation, to which they are connected via N-H···O hydrogen bonds. [ABSTRACT FROM AUTHOR]

Polyoxometalates A series of mixed‐valence Mn6‐sandwiched polyoxometalates (POMs) with SMM behavior have been hydrothermally made, in which the covalently functionalized Mn6 cluster via organic ligands are first observed in POMs. For more details, see the Full Paper by J.‐W. Zhao, G.‐Y. Yang, H.‐S. Liu et al. on page 12322 ff. [ABSTRACT FROM AUTHOR]