Giant Anisotropic Thermal Expansion Phase Transition of Silver Iodide Anionic Organic-Inorganic Hybrid.

Hybrid metal halide materials with charming phase transition behaviors have attracted considerable attention. In former works, much attention has been focused on the phase transition triggered by the order-disorder or displacement motions of the organic component. However, manipulating the variation of the inorganic component to achieve the phase transition has rarely been reported. Herein, two novel organic-inorganic hybrid materials, [THPM]n[AgX2]n (THPM = 3,4,5,6-tetrahydropyrimidin-1-ium, X = I for 1 and Br for 2) with the [AgX2]nn- anionic chain structure, were synthesized. At 293 K, the [AgX2]nn- chains in 1 were constructed by the tetramer units of Ag atoms, while that in 2 was assembled by the dimer structure. Upon heating to 355 K, owing to the variation of the metallophilic interaction between adjacent Ag atoms, a unique transformation process from tetramer to dimer in [AgI2]nn- chains of 1 can be detected and endow 1 with a giant anisotropic thermal expansion with linear strain of ∼7% and shear strain of ∼20%, which can be used as a mechanical actuator for switching. Alternatively, for 2, no phase transition process can be observed upon the temperature variation. This work provides an effective approach to design phase transition materials triggered by the inorganic part.

Building Co16-N3-Based UiO-MOF to Expand Design Parameters for MOF Photosensitization.

The construction of secondary building units (SBUs) in versatile metal-organic frameworks (MOFs) represents a promising method for developing multi-functional materials, especially for improving their sensitizing ability. Herein, we developed a dual small molecules auxiliary strategy to construct a high-nuclear transition-metal-based UiO-architecture Co16-MOF-BDC with visible-light-absorbing capacity. Remarkably, the N3 - molecule in hexadecameric cobalt azide SBU offers novel modification sites to precise bonding of strong visible-light-absorbing chromophores via click reaction. The resulting Bodipy@Co16-MOF-BDC exhibits extremely high performance for oxidative coupling benzylamine (~100 % yield) via both energy and electron transfer processes, which is much superior to that of Co16-MOF-BDC (31.5 %) and Carboxyl @Co16-MOF-BDC (37.5 %). Systematic investigations reveal that the advantages of Bodipy@Co16-MOF-BDC in dual light-absorbing channels, robust bonding between Bodipy/Co16 clusters and efficient electron-hole separation can greatly boost photosynthesis. This work provides an ideal molecular platform for synergy between photosensitizing MOFs and chromophores by constructing high-nuclear transition-metal-based SBUs with surface-modifiable small molecules.

Dielectric and Magnetic Relaxations Exhibited in a 2D Parallel Interpenetrating Frustrated Star Net.

Constructing multiple functional geometric frustration magnets is a hot topic in solid state chemistry and material science. Herein, a two-dimensional (2D) parallel interpenetrating "star" net complex [HDMPDA][Fe6 (µ3 -O)2 (µ-O2 CH)15 ] (1) was obtained successfully with HDMPDA (DMPDA=N, N'-dimethyl-1,3-propanediamine) as charge balancer. The dipole reorientation of the rotator [HDMPDA]+ in the complex brings a structure transition which leads dielectric relaxation close to room temperature. Despite strong antiferromagnetic coupling existing between ions in the net, long-range order temperature TN of the complex is suppressed to 4.2 K by geometric frustration. Interestingly, below TN , a canted antiferromagnetic state, accompanied with slow magnetic relaxation, is detected due to the lack of enough magnetic coupling between 2D layers. Thus, 1 is a particular multifunctional magnetic frustration material containing two different types of relaxations.

Single Crystal to Single Crystal Transformation of CuII Complexes Induced by Dehydrating and Hydrating of Ligands with Chroma Rewritable Behaviors.

In this work, the single crystal to single crystal (SCSC) transformations in three mononuclear copper complexes [CuL22]Cl2·2H2O (1), [CuL12Cl2] (2), and [CuL22]Cl2·4H2O (3) (L1 = di-2-pyridyl ketone, L2 = di(pyridin-2-yl)methanediol) are realized by the irreversible dehydration and hydration reaction of L1 and L2. Dark purple crystal 1 is obtained by self-assembly of L1 and CuCl2·2H2O in solvothermal reactions, in which the carbonyl group of L1 undergoes a hydration addition reaction to form L2. On heating, 1 transforms to 2 by dehydrating water accompanied by the change of the color and coordination octahedron of CuII ions. In a saturated water vapor environment, 2 can absorb six water molecules and transform to 3 with the same color and coordination environment with 1 but different lattice water. The SCSC process from 2 to 3 is reversible: 3 can transform back to 2 on heating like that of 1. Chroma rewritable behaviors in the structural transformation of the complexes make them visually identifiable temperature or water probes.

[Ba4Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba4Cl][M3(HCO2)13]}n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties.

Novel 3D metal formate frameworks {[Ba4Cl][M3(HCO2)13]}n (M = Mn for 1, Co for 2, and Mg for 3) were successfully assembled via microwave-assisted synthesis. The complexes are rare coordination polymers crystallized at space group P4cc with the polar point group C4v. In the structure, the MII ions are bridged by two types of anti-anti formate in forming a 3D pcu framework, and additional formates coordinate to the unsaturated sites of the MII ions in the framework, giving an anionic M-formate net. Ba4Cl clusters take the cavities of the net as charge balance, in which the chloride ion deviates from the center of the barium ions. The asymmetric Ba4Cl structure is transmitted throughout the crystal resulting in polar structure, which is further confirmed by nonlinear optical and piezoelectric test. Nonlinear optical activity tests of 1 and 3 show SHG signals 0.32 and 0.28 times that of KDP, while 2 has a piezoelectric coefficient d33 of 6.8 pC/N along polar axis. Magnetic studies reveal antiferromagnetic coupling between MII ions in 1 and 2. Spin canting was found only in 2 with anisotropic CoII ions, and 2 is a canted antiferromagnetically with TN = 5 K. Further field-induced spin flop was also found in 2 with a critical field 0.9 T.

Dicarboxylate Modulating Molecular-Ionic Platinum Compounds with Variable Stacking and Photoluminescence.

Under solvothermal conditions, 10 molecular-ionic platinum compounds [Pt(NIA)2]·(L)·nH2O (L = dicarboxylate) were synthesized. In the reaction, acetonitrile undergoes trimerization in situ to generate N-(1-iminoethyl)acetamidine (NIA), which coordinates to PtII ions in forming the N-(1-iminoethyl)acetamidine platinum cation, while the organic carboxylates act as anions. Structural analysis shows that carboxylate ligands regulate the mode of packing of [Pt(NIA)2] in those compounds. Photoluminescence studies show that the photoluminescence behaviors of those compounds also depended on the carboxylate ligands. 1-4, 6, and 7 show blue light emission with fluorescence emission wavelengths of 437-440 nm despite the different carboxylate ligands used. 5 and 8 show green emissions with maximum intensity peak positions of 522 nm. Compared with that of 5 and 8, the emission of 9 and 10 has the same red shifts with peak positions of 567 and 528 nm. The variable-temperature photoluminescence studies reveal that 8 and 10 show two different thermal quenching (TQ) zones in the range of 80-420 K, while the emission intensity of 9 shows negative thermal quenching at low temperatures of 80-220 K and TQ in the range of 220-420 K.

Circulating Tumor Cells Expressing Krüppel-Like Factor 8 and Vimentin as Predictors of Poor Prognosis in Pancreatic Cancer Patients.

BACKGROUND: Circulating tumor cells (CTCs) with an epithelial-mesenchymal transition phenotype in peripheral blood may be a useful marker of carcinomas with poor prognosis. The aim of this study was to determine the prognostic significance of CTCs expressing Krüppel-like factor 8 (KLF8) and vimentin in pancreatic cancer (PC). METHODS: CTCs were isolated by immunomagnetic separation from the peripheral blood of 40 PC patients before undergoing surgical resection. Immunocytochemistry was performed to identify KLF8+ and vimentin+ CTCs. The associations between CTCs and time to recurrence (TTR), clinicopathologic factors, and survival were assessed. Univariate and multivariate analyzes were performed to identify risk factors. RESULTS: Patients with CTCs (n = 30) had a higher relapse rate compared to those without (n = 10) (70.0% vs 20.0%; P < 0.01). The proportion of KLF8+/vimentin+ CTCs to total CTCs was inversely related to TTR (r = -0.646; P < 0.01); TTR was reduced in patients with > 50% of CTCs identified as KLF8+/vimentin+ (P < 0.01). Independent risk factors for recurrence were perineural invasion and > 50% KLF8+/vimentin+ CTCs (both P < 0.05). CONCLUSION: Poor prognosis can be predicted in PC patients when > 50% of CTCs are positive for KLF8 and vimentin.

Tunable Ferromagnetic Strength in Niccolite Structural Heterometallic Formate Framework Based on Orthogonal Magnetic Orbital Interactions.

A series of heterometallic formate framework templated by amines were solvothermally prepared. They feature the formula of [AI][CrMII(HCO2)6] (AI = NH4H2OI and M = Mn for 1, AI = CH3NH3I and M = Fe for 2, AI = CH3NH2CH3I and M = Co for 3, AI = CH3NH3I and M = Ni for 4). The title compounds exhibit isostructural niccolite architectures with differences only in the host metal ions and guest amines. Tunable ferromagnetic (FO) strength was realized in the resulting framework under the guidance of orthogonal magnetic orbital analysis of CrIII (t2g3eg) and MII (t2g3eg2 for MnII, t2g4eg2 for FeII, t2g5eg2 for CoII, t2g6eg2 for NiII) ions. The magnetic ordering temperatures derived from the experimental magnetic measurements for 1-4 are lower than 2, 10.3, 7.6, and 22.0 K, respectively. Notably, thanks to the weak FO coupling between CrIII and MnII ions, compound 1 displays a large magnetocaloric effect bearing the maximum of magnetic entropy change (-Δ Smmax) up to 43.9 J kg-1 K-1 with Δ H = 7 T and T = 3.5 K, larger than most reported transition metal-based complexes and commercial gadolinium gallium garnet (Gd3Ga5O12) (-Δ Smmax = 38.4 J kg-1 K-1 with Δ H = 7 T). From 1, 2/3, to 4, an enhancement of the magnetic ordering temperature is observable due to the increasing strength of FO interactions between CrIII and MII ions. Our work provides a successful instance to modulate the strength of FO exchange via analyzing the orthogonal magnetic orbitals of heterometallic ions.

Specific CYP450 Genotypes in the Chinese Population Affect Sorafenib Toxicity in HBV/HCV-associated Hepatocellular Carcinoma Patients.

OBJECTIVE: The purpose of this study was to screen for frequencies of different CYP450 genotypes in the Chinese population and explore the relationship between sorafenib toxicity and CYP450 polymorphism. METHODS: A total of 600 peripheral blood samples were obtained from two groups for this study. The first group of 300 samples were from Chinese patients with HBV/HCV-associated HCC, while the remaining 300 samples were from a healthy population of recruited subjects. Allele-specific PCR and long-fragment gene sequencing was used to identify the frequencies of CYP450 polymorphism. Aflatoxin-induced HCC rat models expressing CYP3A4*1, CYP3A5*3, CYP2C19*2, and CYP2D6*10 were established and treated with sorafenib at certain time points. Hepatic and renal function, along with plasma concentration of sorafenib, were monitored regularly. RESULTS: The most common forms of CYP mutations in the Chinese population were identified. The levels of sorafenib plasma concentration, as well as damage to hepatic and renal function in aflatoxin-induced HCC rat models varied significantly across the different CYP genotypes. CONCLUSION: The mutational frequencies of CYP3A5, CYP3A4, CYP2C19, and CYP2D6 genotypes varied among different ethnic groups and populations. Individuals with CYP3A5*3 demonstrated minimal sorafenib metabolism, which led to severe hepatic and renal damage. Inter-individual variability in sorafenib-toxicity may be interpreted by CYP450 genetic polymorphisms, suggesting that identification of CYP polymorphism within a certain population should be considered in sorafenib therapy.

The Design of Dual-Emissive Composite Material [Zn2(HL)3]+@MOF-5 as Self-Calibrating Luminescent Sensors of Al3+ Ions and Monoethanolamine.

Introducing another chromophore into a luminescent MOF is a potential way to assembling novel dual-emissive luminescent materials. Putting the chromophore, for which luminescence can be enhanced by Zn2+ ion, into MOF-5 by the "bottle around ship" strategy is a simple but efficient synthesis method to realize such dual-emissive materials. According to this strategy, a novel dual-emissive luminescent composite material [Zn2(HL)3]+@MOF-5 was constructed by loading the [La3(HL)2L2(NO3)3H2O] (1) (H2L = 7,7'-(ethane-1,1'-diyl)8-hydro-quinoline) into MOF-5, in which the [Zn2(HL)3]+ anions were transformed from 1 with the existence of Zn2+. The dual-emissive composite materials show excellent luminescence with two emissions of MOF-5 at 410 nm and [Zn2(HL)3]+ at 524 nm. Furthermore, by combining characteristics of MOF-5 and the guest chromophore, the composite material is highly selectively sensitive toward Al3+ and monoethanolamine, which makes [Zn2(HL)3]+@MOF-5 a potential self-calibrated fluorescence sensor.

Gadolinium sulfate modified by formate to obtain optimized magneto-caloric effect.

Three new Gd(III) based coordination polymers [Gd2(C2H6SO)(SO4)3(H2O)2]n (1), {[Gd4(HCOO)2(SO4)5(H2O)6]·H2O}n (2), and [Gd(HCOO)(SO4)(H2O)]n (3) were obtained by modifying gadolinium sulfate. With the gradual increase of the volume ratio of HCOOH and DMSO in synthesis, the formate anions begin to coordinate with metal centers; this results in the coordination numbers of sulfate anion increasing and the contents of water and DMSO molecules decreasing in target complexes. Accordingly, spin densities both per mass and per volume were enhanced step by step, which are beneficial for the magneto-caloric effect (MCE). Magnetic studies reveal that with the more formate anions present, the larger the negative value of magnetic entropy change (-ΔSm) is. Complex 3 exhibits the largest -ΔSm = 49.91 J kg(-1) K(-1) (189.51 mJ cm(-3) K(-1)) for T = 2 K and ΔH = 7 T among three new complexes.

Design and synthesis of stable cobalt-based weak ferromagnetic framework with large spin canting angle.

It still remains a great challenge to design and construct framework-structured weak ferromagnets with large canting angle which is an effective approach for high performance magnets. According to the strategy of antisymmetric interaction causing spin canting, we report the design of four cobalt compounds, which were tested by X-ray single crystal diffraction, TGA, PXRD, and magnetic measurement. Single-crystal structure analysis reveals that compound 1 has a 2D structure, complex 2 has a 3,4-connected 3D framework, and complex 3 exhibits a 3D net structure with rare 3,5-connected 2-nodal ß-SnF2 topology and the solvent MeOH trapped in the 3D channels as guests. The magnetic property of 3 is spin canting just as designed, with TN about 4.0 K and large canting angle of 14.8°. Highly stable compound 3 sustains its framework in air for more than 12 months, in which the guest MeOH molecules can be replaced by water to form complex 4.

Diverse Hap43-independent functions of the Candida albicans CCAAT-binding complex.

The CCAAT motif is ubiquitous in promoters of eukaryotic genomes. The CCAAT-binding complex (CBC) is conserved across a wide range of organisms, specifically recognizes the CCAAT motif, and modulates transcription directly or in cooperation with other transcription factors. In Candida albicans, CBC is known to interact with the repressor Hap43 to negatively regulate iron utilization genes in response to iron deprivation. However, the extent of additional functions of CBC is unclear. In this study, we explored new roles of CBC in C. albicans and found that CBC pleiotropically regulates many virulence traits in vitro, including negative control of genes responsible for ribosome biogenesis and translation and positive regulation of low-nitrogen-induced filamentation. In addition, C. albicans CBC is involved in utilization of host proteins as nitrogen sources and in repression of cellular flocculation and adhesin gene expression. Moreover, our epistasis analyses suggest that CBC acts as a downstream effector of Rhb1-TOR signaling and controls low-nitrogen-induced filamentation via the Mep2-Ras1-protein kinase A (PKA)/mitogen-activated protein kinase (MAPK) pathway. Importantly, the phenotypes identified here are all independent of Hap43. Finally, deletion of genes encoding CBC components slightly attenuated C. albicans virulence in both zebrafish and murine models of infection. Our results thus highlight new roles of C. albicans CBC in regulating multiple virulence traits in response to environmental perturbations and, finally, suggest potential targets for antifungal therapies as well as extending our understanding of the pathogenesis of other fungal pathogens.

Advances in the differentiation of pluripotent stem cells into vascular cells.

Blood vessels constitute a closed pipe system distributed throughout the body, transporting blood from the heart to other organs and delivering metabolic waste products back to the lungs and kidneys. Changes in blood vessels are related to many disorders like stroke, myocardial infarction, aneurysm, and diabetes, which are important causes of death worldwide. Translational research for new approaches to disease modeling and effective treatment is needed due to the huge socio-economic burden on healthcare systems. Although mice or rats have been widely used, applying data from animal studies to human-specific vascular physiology and pathology is difficult. The rise of induced pluripotent stem cells (iPSCs) provides a reliable in vitro resource for disease modeling, regenerative medicine, and drug discovery because they carry all human genetic information and have the ability to directionally differentiate into any type of human cells. This review summarizes the latest progress from the establishment of iPSCs, the strategies for differentiating iPSCs into vascular cells, and the in vivo transplantation of these vascular derivatives. It also introduces the application of these technologies in disease modeling, drug screening, and regenerative medicine. Additionally, the application of high-tech tools, such as omics analysis and high-throughput sequencing, in this field is reviewed.

Lipid metabolism of hepatocellular carcinoma impacts targeted therapy and immunotherapy.

Hepatocellular carcinoma (HCC) is a common malignant tumor that affecting many people's lives globally. The common risk factors for HCC include being overweight and obese. The liver is the center of lipid metabolism, synthesizing most cholesterol and fatty acids. Abnormal lipid metabolism is a significant feature of metabolic reprogramming in HCC and affects the prognosis of HCC patients by regulating inflammatory responses and changing the immune microenvironment. Targeted therapy and immunotherapy are being explored as the primary treatment strategies for HCC patients with unresectable tumors. Here, we detail the specific changes of lipid metabolism in HCC and its impact on both these therapies for HCC. HCC treatment strategies aimed at targeting lipid metabolism and how to integrate them with targeted therapy or immunotherapy rationally are also presented.

Prognostic Analysis of Single Large Hepatocellular Carcinoma Following Radical Resection: A Single-Center Study.

Objective: To investigate the survival and independent prognostic factors for single large hepatocellular carcinoma (SLHCC) after surgical resection. Methods: Patients with SLHCC who underwent radical resection from January 2013 to December 2017 were retrospectively analyzed. The Kaplan-Meier method was used to analyze the overall survival (OS) rate and recurrence-free survival (RFS) rates. Cox forward stepwise regression was performed to analyze the independent prognostic factors. Results: A total of 485 cases were included. The average age was 51.2±11.2 years, 88.9% had a history of hepatitis B virus infection, and most patients had normal liver function. The average tumor diameter was 8.8±3.0 cm. The 1-, 3-, and 5-year OS and RFS rates were 76.8%, 56.7%, and 45.7%, and 61.0%, 46.2%, and 34.7%, respectively. Multivariate analysis showed that liver cirrhosis (HR=1.456, P=0.004), total bilirubin (TB) ≥17.1 µmol/L (HR=1.437, P=0.011), glutamyl transferase (GGT) >60 U/L (HR=1.438, P=0.020), lactate dehydrogenase (LDH) >225 U/L (HR=1.442, P=0.007), blood loss ≥400 mL (HR=1.339, P=0.027), microvascular invasion (MVI) (HR=1.492, P=0.004), satellite lesions (HR=1.859, P<0.0001) and Edmondson-Steiner grade III+IV (HR=1.740, P=0.018) were independent risk factors for reduced OS in SLHCC patients. Sex (HR=1.763, P=0.003), liver cirrhosis (HR=1.382, P=0.007), GGT >60 U/L (HR=1.512, P=0.003), LDH >225 U/L (HR=1.480, P=0.002), MVI (HR=1.545, P=0.001), and satellite lesions (HR=1.564, P=0.001) were independent risk factors for reduced RFS. OS and RFS nomograms were constructed using risk factors with C-index values of 0.692 (95% CI: 0.659-0.724) and 0.659 (95% CI: 0.623-0.693), respectively. The Hosmer-Leme test demonstrated the good fit of both nomograms. Conclusion: Surgical resection is the standard and effective treatment for SLHCC patients. Sex, liver cirrhosis, TB≥17.1 µmol/L, GGT>60 U/L, LDH>225 U/L, blood loss≥400 mL, MVI, Edmondson-Steiner grade III+IV, and satellite lesions were found to be independent prognostic factors in SLHCC patients following radical resection. The OS and RFS nomograms accurately predicted the prognosis of SLHCC patients.

Effects of low environmental salinity on the cellular profiles and expression of Na+, K+-ATPase and Na+, K+, 2Cl- cotransporter 1 of branchial mitochondrion-rich cells in the juvenile marine fish Monodactylus argenteus.

The goal of this study was to determine the osmoregulatory ability of a juvenile marine fish, silver moony (Monodactylus argenteus), for the purpose of developing a new experimental species for ecophysiological research. In this study, M. argenteus was acclimated to freshwater (FW), brackish water (BW), or seawater (SW). The salinity tolerance of this euryhaline species was effective, and the fish survived well upon osmotic challenges. The largest apical surface of mitochondrion-rich cells was found in the FW individuals. Immunohistochemical staining revealed that Na(+), K(+)-ATPase immunoreactive (NKA-IR) cells were distributed in the interlamellar region of the gill filaments of the silver moony in all experimental groups. In addition to the filaments, NKA-IR cells were also found in the lamellae of the FW individuals. The number of NKA-IR cells in the gills of the FW individuals exceeded that of the BW and SW individuals. The NKA-IR cells of FW and SW individuals exhibited bigger size than that of BW fish. The NKA activities and protein expression of the NKA α-subunit in the gills of the FW individuals were significantly higher than in the BW and SW groups. Additionally, the relative amounts of Na(+), K(+), 2Cl(-) cotransporter 1 (NKCC1) were salinity-dependent in the gills. Immunofluorescent signals of NKCC1 were localized to the basolateral membrane of NKA-IR cells in all groups. In the gills of the FW individuals, however, some NKA-IR cells did not exhibit a basolateral NKCC1 signal. In conclusion, the present study illustrated the osmoregulatory mechanisms of this easy- and economic-to-rear marine teleost with euryhaline capacity and proved the silver moony to be a good experimental animal.

catena-Poly[[(1,10-phenanthroline)cobalt(II)]-di-µ-azido].

In the crystal structure of the binuclear title complex, [Co(N(3))(2)(C(12)H(8)N(2))](n), each Co(II) cation is coordinated by two N atoms from one chelating 1,10-phenanthroline ligand and four azide ligands in a slightly distorted octa-hedral coordination. The two Co(II) cations of the binuclear complex are related by an inversion centre and are bridged by two symmetry-related azide ligands in both µ(1,1) and µ(1,3) modes. The µ(1,3) bridging mode gives rise to an infinite one-dimensional chain along the a axis, whereas the µ(1,1) bridging mode is responsible for the formation of the binuclear Co(II) complex.

Tetra-µ-benzoato-bis-[(3,5-dimethyl-pyridine)-copper(II)].

In the centrosymmetric binuclear title compound, [Cu(2)(C(7)H(5)O(2))(4)(C(7)H(9)N)(2)], the Cu(II) atom is coordinated by four O atoms from benzoate anions and one N atom from a dimethyl-pyridine ligand. A paddle-wheel-like dimer is formed by two Cu(II) ions and four benzoate anions with two 3,5-dimethyl-pyridine ligands at the axial position of the Cu(II) ions. The dihedral angle between the two unique benzene rings is 84.26 (16)°. The dihedral angles between the pyridine ring and the benzene rings are 61.67 (15) and 34.27 (14)°. There is π-π stacking of inversion-related pyridine rings, with a centroid-centroid distance of 3.833 (2) Å.

Supramolecular isomorphic dodecanuclear cobalt clusters with the same metal shell but different core ligands.

In this work, we report two supramolecular isomorphic dodecanuclear cobalt complexes, [Co12(mtz)3(L)6(NO3)2(OH)(N3)3]·(OH)3 (1) and [Co12(mtz)3(L)6(NO3)2(OH)(N3)(OAc)]·(OH)4 (2), (Hmtz = 5-methyl-1H-tetrazole, H2L = 7,7'-(ethane-1,1-diyl) diquinolin-8-ol) crystallizing in the P̄ space group with the same unit cell parameters. In 1 and 2, two pirate hat-like hexanuclear Co6(NO3)(L)3 units form the same dodecanuclear metal shell, but the ligands between the hexanuclear units as the core are distinct. The introduction of acetate anions leads to a blue shift of the absorption band in the visible region. Magnetism studies indicate an antiferromagnetic interaction between the CoII ions in the clusters.