Dumbbell-shaped Zn(ii) paddlewheel dimers bearing pi-extended triphenylamine-ethynylpyridine ligands were synthesized to investigate how fluorination and axial pi-extension influence structural flexibility and luminescence responsiveness. Single-crystal X-ray diffraction revealed that the benzoate and pentafluorobenzoate derivatives retain the Zn2(mu-carboxylate)4 core but differ in carboxylate planarity, intermolecular contacts, and overall molecular distortion. These subtle structural variations strongly affect their excited-state landscapes. The fluorinated complex exhibits an additional intramolecular charge-transfer absorption band and enhanced electronic anisotropy, leading to pronounced changes in the solid-state emission. Both complexes display reversible mechanochromic luminescence associated with partial amorphization and recrystallization, while the fluorinated derivative undergoes a larger red shift and higher quantum yield after grinding. High-pressure photoluminescence measurements on single crystals revealed continuous and nearly reversible emission shifts. The fluorinated complex shows a substantial 83 nm shift (Delta E = 0.36 eV) and a full multicolor progression from green to orange-red up to 3.6 GPa, whereas the non-fluorinated analogue displays only modest changes. These behaviors demonstrate that fluorination increases structural flexibility and enhances the pressure adaptability of the Zn2 core. The results establish a design strategy in which a d10 metal scaffold is combined with electronically tunable pi-extended axial ligands to achieve multicolor, reversible, and stimuli-responsive luminescence in simple molecular assemblies.

The temperature and pressure dependence of the crystal structures and photophysical properties of three crystalline polymorphs of imidoylamidinato Pt(II) complexes exhibiting green luminescence (UG form, main phase), yellow luminescence (UY form), and orange luminescence (UO form) under ambient temperature and pressure were investigated. While the UG and UO forms did not show phase transitions in the temperature range of 300-90 K and below 6.5 GPa (UG) or 3.2 GPa (UO), the UY form exhibited inverse symmetry breaking induced by temperature and pressure. Based on observations of temperature- and pressure-induced phase transition processes using single-crystal X-ray diffraction and optical microscopy, these phase transitions were confirmed to proceed in a single-crystal to single-crystal manner via a twinning deformation process, in which multiple structural domains corresponding to different phases coexisted simultaneously within individual crystal particles during the transformation. It was revealed that, in the UY form, the strength of the interaction between BF4- ions and complex cations changes with temperature and pressure. This triggers a phase transition by inducing alterations in the arrangement of complex cations and counter-anions. In terms of contracting the crystal lattice, the effects of cooling and pressurization are similar. However, observing different luminescence behaviors in the UO and UY forms under temperature and pressure changes revealed that temperature and pressure do not necessarily have consistent effects on the stability of the excited state.

A series of chloridotricarbonyl rhenium(I) complexes with azolylpyridines, [ReCl(CO)3(H-N2py)] (1-H, H-N2py = 2-(3-pyrazolyl)pyridine), [ReCl(CO)3(H-N3py)] (2-H, H-N3py = 2-[1,2,3]-triazol-4-yl-pyridine), and [ReCl(CO)3(N4py)]- ([3]-, N4py- = 2-(tetrazol-5-yl)-pyridine anion) was synthesized and characterized. The pKa values of the complexes were determined by UV-vis titration to be 7.57 ± 0.50 for 1-H and 4.29 ± 0.23 for 2-H, whereas those for the reported H-N2py and H-N3py coordinate Re(V) complexes, [ReN(CN)3(H-N2py)]- and [ReN(CN)3(H-N3py)]-, were 9.20 ± 0.10 and 4.90 ± 0.20, respectively. The {ReCl(CO)3} unit exhibited a larger electron-accepting ability of the complex unit than {ReN(CN)3}-. Protonation did not occur in the reaction of [3]- with p-toluenesulfonic acid in dimethylsulfoxide (DMSO). All new complexes exhibited photoluminescence in DMSO and the crystalline phase at 298 K. The temperature dependences of the emission spectra and emission lifetimes of the crystalline samples were measured. An investigation of temperature sensor performance based on temperature dependent emission lifetimes revealed that the complexes exhibited distinct temperature ranges. The emission intensities of 1-H and 2-H decreased significantly upon deprotonation of the coordinated azolylpyridines, with slight shifts of the maximum emission wavelengths.

A series of organic crystalline solids is prepared by Lewis pairing the pyridyl derivatives of benzothienobenzothiophene (BTBT) and tris(pentafluorophenyl)borane (TPFB). The Lewis pair series shows structural variations in the arrangements of the BTBT moiety: 1D pi-stacked columns covered by TPFB, slipped columns, and cofacial dimers. Quantum chemical calculations are performed to quantify the intermolecular electronic coupling and bandgaps, which reveal that the 1D columns are electronically fragmented at the dimer or tetramer level. In response to the degree of electronic aggregations, the Lewis pairs exhibit red-shifted fluorescence, reaching 5810 cm-1 from the emission maximum of the non-substituted BTBT (397 nm) to that of one crystal form (516 nm). Scanning tunneling microscopy reveals that one Lewis pair is loosely gathered on the Ag(111) surface without any ordered arrangement of the adsorbates, differing from that in the solid phase. Furthermore, vibrational fingerprinting of the Lewis pair is achieved using tip-enhanced Raman scattering techniques at the single-molecule level, including the B-N and C-S stretching characteristics. These results provide insight into modulating the molecular arrangements of small-molecule semiconducting units to alter the emission properties, as well as fabricating molecular devices adsorbed on surfaces via post-modification.

In adults, expressed in renal cancer (ERC)/mesothelin is exclusively expressed in the mesothelial cells lining the pleural, pericardial, and peritoneal cavities, yet its function under physiological conditions is unknown. To explore this, we studied ERC expression in wild-type (WT) mice at different developmental stages by immunohistochemistry and analyzed the ultrastructure of the mesothelium in WT and Erc-knockout (KO) mice via electron microscopy. Additionally, cardiopulmonary function in adult WT and Erc-KO mice was assessed using echocardiography and the forced oscillation technique (FOT). During embryonic development in WT mice, ERC expression was detected in the epicardium as early as embryonic day (E)12.5 but was absent in the pleura until E18.5. The timing of expression appeared to coincide with the active maturation of these organs, which implied a potential role in cardiopulmonary development. Electron microscopy revealed that microvilli on the mesothelium of Erc-KO mice were immature compared to those of WT mice. Based on these findings, we hypothesized that ERC might contribute to cardiopulmonary function; however, echocardiography and FOT did not reveal any functional differences between WT and Erc-KO mice. This suggests that ERC has limited functional relevance under physiological conditions.

Benzothienobenzothiophene (BTBT) has attracted increasing attention as an organic semiconducting molecular scaffold. This paper presents the synthesis and characterization of a covalent conjugate of BTBT and ferrocene (FcH). Target conjugate 1 was characterized through 1H NMR and UV-vis absorption spectroscopies and compared with its parent components, FcH and BTBT. Compound 1 exhibited a highly reversible Fe(III)/Fe(II) redox couple, in accordance with the redox properties inherited from FcH. The Fc-based characteristics of 1 were consistent with DFT calculation data, indicating that the HOMO of 1 is primarily localized on the Fc moiety, with some distribution on the BTBT moiety. Single-crystal X-ray diffraction revealed that 1 possesses molecular packing associated with intermolecular homointeractions (FcFc and BTBTBTBT) and heterointeractions (FcBTBT) in the solid state. In the DFT-optimized structure of the one-electron-oxidized species 1 + , both the positive charge and LUMO were predominantly localized on the Fc moiety. In solution, 1 + exhibited intramolecular charge transfer (ICT) transition absorption from the BTBT to the Fc+ moiety. These results provide insights into the functionalization of small-molecule organic semiconducting scaffolds with organometallic fragments, as well as the evaluation of the properties of the resulting conjugates toward molecular electronics.

Fluorescence (FL) properties of crystals of [2.2]paracyclophane-containing organoboron complexes (pCP-H and pCP-iPr) were investigated under high pressure using a diamond anvil cell to evaluate the effects of intramolecular pi-pi interactions in the [2.2]paracyclophane moiety on piezofluorochromism (PFC). Crystals of both pCP-H and pCP-iPr were found to display remarkable PFC with redshifts of more than 100 nm under high pressures up to ca. 8 GPa. However, the pressure-sensitivities of FL of pCP-H and pCP-iPr crystals differed. The results of X-ray crystallography studies under ambient and high pressure revealed that PFC of the pCP-H crystal mainly originates from intermolecular pi-pi interactions taking place in a pi-stacked dimer. Density functional theory calculations also showed that intermolecular orbital interactions in the pi-stacked dimer play an important role in the PFC of pCP-H. In contrast, it was found that pCP-iPr does not form a pi-stacked dimer in the crystal state. Therefore, PFC of the pCP-iPr crystal is mainly controlled by intramolecular pi-pi interactions in the [2.2]paracyclophane moiety, making it less sensitive than pCP-H to pressure changes.

Natural killer (NK)/T-cell lymphomas are a highly aggressive lymphoma subtype common in East Asia and Latin America. To develop a therapeutic monoclonal antibody (mAb) against it, BALB/c mice were alternately immunized with two vigorous NK lymphoma cell lines. After hybridization, culture supernatants of the hybridoma clones were added to a third NK lymphoma cell line not used for immunization, and the antibodies were screened for direct cytolytic activity. Results showed that the newly established mAb, named mAb ANAP, induced immediate cell death against NK lymphoma cells in a cytoskeleton-dependent manner, which was also complement-, antibody-dependent cell-mediated cytotoxicity-, and caspase-independent, forming large pores on target cell surface within 20 min; mAb ANAP did not injure normal cells and could bind to the ITGA4 (CD49d). Contrary to existing anti-ITGA4 antibodies, which did not exhibit any destructive activity against NK lymphoma, ANAP antibody has promising potential as a therapeutic agent for NK lymphoma.

Two-dimensional (2D) metal-organic frameworks (MOFs) are a class of materials exhibiting various functionalities based on anisotropic layered structures constructed through strong in-plane connectivity and weak van der Waals interlayer interaction. However, their anisotropic mechanical properties and modulation of 2D-MOF crystals have been rarely investigated. Herein, we report the compression and elastic properties of two 2D-MOFs, [Mn(salen)](2)[Pt(CN)(4)]H2O (1) and [Mn(salen)](2)[PtI2(CN)(4)]H2O (2), composed of undulating layers. These layers were highly compressive due to the undulation changes whose compressibility were much larger than those of other crystalline 2D materials. 1 and 2 incorporated structural differences involving the zigzag angles of undulating layers, leading to opposite trends in anisotropic compressibility caused by compression-induced structural transformation between flattening and rippling of the layers. In addition, by conducting high-pressure experiments for 1 using two different pressure-transmitting media (oils or alcohols), we found that ethanol molecules were introduced into the interlayer spaces, unlike oils. This hyperfilling phenomenon resulted in an anisotropic structural transformation involving an expansion along the layer-stacking direction under high pressures. Furthermore, these compression behaviors were impacted by the crystal morphology, such as single crystals and powder forms. Moreover, the Young's moduli in (110) and (001) directions of 1 and 2 were evaluated by nanoindentation experiments, demonstrating the mechanical flexibility of the wavy cyanido-bridged chains.

Crystallization of the title compound, fac-[ReBr(ppt-OMe)(CO)3] (ppt-OMe = C15H12N2OS), from CH2Cl2/n-pentane (1:5 v/v) at room temperature gave two polymorphs, which crystallize in monoclinic (P21/c; α form) and orthorhombic (Pna21; β form) space groups. The ReI complex molecules in either polymorph adopt a six-coordinate octahedral geometry with three facially-oriented carbonyl ligands, one bromido ligand, and two nitrogen atoms from one chelating ligand ppt-OMe. In the crystal, both polymorph α and β form di-periodic sheet-like architectures supported by multiple hydrogen bonds. In polymorph α, two types of hydrogen bonds (C—H...O) are found while, in polymorph β, four types of hydrogen bonds (C—H...O and C—H...Br) exist.

A cyclometalated Pt(II) complex was synthesized by appending a pyridyl ligand containing a benzothienobenzothiophene (BTBT) unit, which is a well-known small organic molecule semiconductor. The target complex [Pt(ppy)(BTBT-py)Cl] (2) was characterized by H-1 NMR, steady-state UV-vis absorption, and photoluminescence spectroscopies in comparison with [Pt(ppy)(ppyH)Cl] (1) and BTBT-py (where ppy = 2-phenylpyridine and BTBT-py = 2-(3-pyridyl)-[1]benzothieno[3,2-b][1]benzothiophene). Complex 2 exhibited absorption bands derived from the ppy-centered pi-pi* transition and intramolecular charge transfer (ICT) from BTBT to pyridine moieties, indicating that 2 inherited the combined properties of the parent complex 1 and the parent ligand BTBT-py. Moreover, DFT calculations showed that 2 inherited HOMO and LUMO characteristics from BTBT-py as well as HOMO-1 and LUMO+1 characteristics from 1. While BTBT-py showed fluorescence from the (ICT)-I-1 state, the corresponding fluorescence was quenched in 2 because the Pt center, a heavy atom, enhanced the intersystem crossing. The ancillary ligand-centered (ICT)-I-3, rather than the ppy-centered (3)pi-pi*, state was successfully monitored in 2 using femtosecond transient absorption spectroscopy. Replacing the phenyl group with the BTBT unit in the cyclometalated Pt(II) complex restructured the electronic structure of the lowest triplet excited state, shifting the centered ligand from ppy to BTBT-py.

Crystallization of the title compound, fac-[ReBr(ppt-OMe)(CO)3] (ppt-OMe = C15H12N2OS), from CH2Cl2/n-pentane (1:5 v/v) at room temperature gave two polymorphs, which crystallize in monoclinic (P21/c; α form) and ortho-rhom-bic (Pna21; β form) space groups. The ReI complex mol-ecules in either polymorph adopt a six-coordinate octa-hedral geometry with three facially-oriented carbonyl ligands, one bromido ligand, and two nitro-gen atoms from one chelating ligand ppt-OMe. In the crystal, both polymorph α and β form di-periodic sheet-like architectures supported by multiple hydrogen bonds. In polymorph α, two types of hydrogen bonds (C-H⋯O) are found while, in polymorph β, four types of hydrogen bonds (C-H⋯O and C-H⋯Br) exist.

Crystallization of the title compound from CH2Cl2/n-pentane (1:5 v/v) at room temperature gave two polymorphs, which crystallize in monoclinic (P21/c; α form) and ortho­rhom­bic (Pna21; β form) space groups. The ReI complex mol­ecules in either polymorph adopt a six-coordinate octa­hedral geometry with three facially-oriented carbonyl ligands, one bromido ligand, and two nitro­gen atoms from one chelating ligand ppt-OMe. In the crystal, both polymorph α and β form di-periodic sheet-like architectures supported by multiple hydrogen bonds.

The molecular architecture of a triruthenium complex and 1,4-di(4-pyridyl)benzene on highly oriented pyrolytic graphite was investigated by drop-casting mixed tetrahydrofuran and methanol solutions. Atomic force microscopy revealed the formation of one-dimensional molecular wires on highly oriented pyrolytic graphite after heating the mixed tetrahydrofuran solution, whereas large ring structures were formed in the methanolic solution. It was found that the molecular architectures composed of triruthenium complexes and 1,4-di(4-pyridyl)benzene strongly depend not only on the temperature of the solution but also on the organic solvents. The formation of the molecular architecture was supported by the ultraviolet-visible absorption spectra of the mixed solution and the electrochemical responses of the deposited film.

Glycosylation changes of cancer cells are known to be associated with malignant progression and metastases and potentially determine the organ-selective nature of metastasis as theorized by Paget (Lancet 1:571–573, 1889). Cellular glycans play a variety of roles in the processes of metastasis and may be unique to the cells that metastasize to different organs. We analyzed the glycosylation profiles of the primary tumor and tumors metastasized to lymph node, liver, lung, brain, bone, thyroid, kidney, adrenal, small intestine and pancreas in an autopsy case of breast cancer employing a lectin microarray with 45 lectins. Clustering analysis of the data revealed that metastatic breast cancer cells were categorized into several clusters according to their glycosylation profiles. Our results provide a biological basis to understand differential phenotypes of metastatic breast cancer cells potentially reflecting clonal origin, which does not directly reflect genomic or genetic changes or microenvironmental effects but connects to glycosylation profiles.

The title complex was newly synthesized by straightforward ligand substitution of a parent complex having a N2P2 set. The present complex had a deformed rhomboidal {Cu2I2} core with shortened CuCu and prolonged II diagonals compared with those of the parent complex and formed one-dimensional channels filled with solvent molecules in crystals. The complex exhibited unusual red shift in solid-state photoluminescence assigned to halogen/metal-to-ligand charge transfer, indicating association of the unique crystal packing containing intramolecular electronic coupling between benzothienobenzothiophene moieties. Graphical Abstract A new iodo-bridged dicopper(I) complex was synthesized by covalently introducing a benzothienobenzothiophene (BTBT) unit in pyridyl ligands-a well-known P-type organic semiconductor. The complex exhibited unusual red shift in solid-state photoluminescence assigned to halogen/metal-to-ligand charge transfer, indicating association of intramolecular electronic coupling between BTBT moieties in the ground state and structural relaxation at the Cu2I2 core in the excited state.

We herein report the synthesis, characterizations, and synchrotron X-ray charge-density studies of oxo-centered triruthenium(II,III,III) clusters [Ru3O(CHCl2COO)(6)(py)(3)] (1) and [Ru3O(CHCl2COO)(6)(CO)(py)(2)] (2) (py = pyridine). Dichloroacetate was chosen for its large scattering factor of the Cl atom, and its electron-withdrawing nature results in significant stabilization of the targeted lower-valent Ru-3(II,III,III) state in the cluster framework. Multipole analysis revealed that the difference in electron populations between two crystallographically independent Ru centers is small for 1 (Delta = 0.30 e) but large for 2 (Delta = 1.46 e). Remarkable differences between 1 and 2 are also found in their static deformation density maps; substantial local charge depletion was found around the central mu O-3 atom for 1, which is less pronounced for 2. According to the topological characterization of Ru-mu O-3 bonds associated with the bond critical point, bcp, the electron density, rho(bcp), is in the range of 0.79-0.89 e & Aring;(-3), and the total energy density, H-bcp, is in the range of -0.21 to -0.05 hartree & Aring;(-3). These findings represent the first charge-density distribution analysis of mixed-valence multinuclear Ru complexes including comparison between 3d and 4d transition-metal systems.

Controlling the self-assembly and nanoarchitectures of metal complexes at the molecular scale is essential for the development of new functional materials and devices. Since two-dimensional (2D) sheets consisting of metal complexes can be designed and controlled with various bonding modes, geometric structures, and chemical functions, they have been studied using various approaches by selecting metal ions and organic ligands. Trinuclear metal clusters contain three metal ions in one complex and are expected to be building blocks for the formation of 2D sheets of metal complexes by selecting their shape and axial ligands. In this study, a trinuclear cluster of ruthenium ions, Ru3O(EtCOO)6(CO)(THF)2:1, was used as the core to form nanostructures on highly oriented pyrolytic graphite (HOPG) substrates via axial ligand exchange with 1,4-Di (4-pyridyl) benzene:2 and 4,4’-di(4-pyridyl) biphenyl: 3. The adlayer structures and electrochemical properties of the nanoarchitectures were investigated by atomic force microscopy (AFM) and cyclic voltammetry (CV). In the experimental procedure, powders of 1, 2, and 3 were dissolved in methanol (MeOH) and tetrahydrofuran (THF), respectively, and a 0.78 µM solution was prepared. A predetermined amount of this was cast on HOPG, dried to form a thin film, and the thin film was observed in air using AFM. Next, equal amounts of 1 and 2 and 1 and 3 solutions were mixed in each solvent, and after heating a water bath at 60°C for 1 h, thin films were prepared in the same manner and observed by AFM. Ultraviolet–visible (UV-vis) absorption spectra and electrochemical measurements by CV were performed before and after heating the mixed solutions. First, in the AFM image of the thin film prepared by casting the MeOH mixture of 1 and 2, two stripe-like domains with different heights were observed, which matched the heights of the structures obtained in the AFM images of the single-domain formation of 1 and 2. In addition, no new absorption peaks were observed in the UV-vis absorption spectrum after mixing the solution; it was inferred that 1and 2 did not exchange ligands. However, when the mixed solution was heated in a water bath for 1 h, a few striped domains were observed, and a new ring-like structure was formed. The CV results also supported the change in the AFM images and absorption spectra after heating the solution. Before heating the mixed solution, a small redox peak was observed around 0.8 V, whereas after the warm bath, a large redox peak was observed around 0.6 V. A dramatic change in the magnitude of the current density was observed, indicating a significant improvement in conductivity. These results suggest that heating the mixed solution replaced THF ligand 1 with 2, forming a cyclic structure consisting of 1 and 2. When the same experiment was carried out in THF solution, a different structure was observed from that of the methanol solution, and a one-dimensional (1D) molecular wire structure was formed after heating the water bath. The absorption spectra and CV results also supported that ligand exchange occurred in the 1D wire structure, revealing the solvent dependence of the nanoarchitecture. When 3 was used as the axial ligand, larger structures were formed compared to 2, and one-dimensional wire structures of several micrometers were observed in the THF solution after the warm bath. Larger current densities and peak separations are also observed in the voltammograms. Thus, the length dependence of the organic ligand for the nanoarchitecture formation on the HOPG surface was demonstrated. Figure 1

Elaborate metal-free electrochemiluminescence (ECL) systems require highly robust organic emitters in the radical form. In their Research Article (e202301109), Keishiro Tahara, Masaaki Abe, and co-workers used the classical Lewis acid B(C6F5)3 as an electrochemical protector of donor–acceptor emitters, leading to the discovery of Lewis-pairing-induced ECL enhancement. The Lewis acid also converted the molecular arrangements of the emitters, playing a unique role in crystalline-film ECL. Elaborate metal-free electrochemiluminescence (ECL) systems require highly robust organic emitters in the radical form. In their Research Article (e202301109), Keishiro Tahara, Masaaki Abe, and co-workers used the classical Lewis acid B(C6F5)3 as an electrochemical protector of donor–acceptor emitters, leading to the discovery of Lewis-pairing-induced ECL enhancement. The Lewis acid also converted the molecular arrangements of the emitters, playing a unique role in crystalline-film ECL. Electrocatalysis Drug Delivery Nanoparticles Metal–Organic Frameworks