In Situ Metal-Assisted Ligand Modification Induces Mn4 Cluster-to-Cluster Transformation: A Crystallography,Mass Spectrometry,and DFT Study

Dehydration of (S,S)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethane-1,2-diol (H₄L) to (Z)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethenol) (H₃L′) was found to be metal-assisted, occurs under solvothermal conditions (H₂O/CH₃OH), and leads to [Mn^II₄(H₃L)₄Cl₂]Cl₂ ⋅ 5 H₂O ⋅ 5 CH₃OH ( Mn₄L₄ ) and [Mn^II₄(H₂L′)₆(μ₃-OH)]Cl ⋅ 4 CH₃OH ⋅ H₂O ( Mn₄L′₆ ), respectively. Their structures were determined by single-crystal XRD. Extensive ESI-MS studies on solutions and solids of the reaction led to the proposal consisting of an initial stepwise assembly of Mn₄L₄ from the reactants via [MnL] and [Mn₂L₂] below 80 °C, and then disassembly to [MnL] and [MnL₂] followed by ligand modification before reassembly to Mn₄L′₆ via [MnL′], [MnL′₂], and [Mn₂L′₃] with increasing solvothermal temperature up to 140 °C. Identification of intermediates [Mn₄L_xL′_6−x] (x=5, 4, 3, 2, 1) in the process further suggested an assembly/disassembly/in situ reaction/reassembly transformation mechanism. These results not only reveal that multiple phase transformations are possible even though they were not realized in the crystalline state, but also help to better understand the complex transformation process between coordination clusters during “black-box” reactions.     

Tuning Electrical- and Photo-Conductivity by Cation Exchange within a Redox-Active Tetrathiafulvalene-Based Metal–Organic Framework

To activate electronic and optical functions of the redox-active metal–organic framework, (Me₂NH₂)[In^III(TTFTB)]⋅0.7 C₂H₅OH⋅DMF (Me₂NH₂@ 1 , TTFTB=tetrathiafulvalene-tetrabenzoate, DMF=N,N-dimethylformamide), has been exchanged by tetrathiafulvalenium (TTF^.+) and N,N′-dimethyl-4,4′-bipyridinium (MV²⁺). These cations provide electron carriers and photosensitivity. The exchange retains the crystallinity allowing single-crystal to single-crystal post-synthetic transformation to TTF@ 1 and MV@ 1 . Both TTF^.+ and MV²⁺ enhance the electrical conductivity by a factor of 10² and the visible light induced photocurrent by 4 and 28 times, respectively. EPR evidences synergetic effect involving charge transfer between the framework redox-active TTFTB bridges and MV²⁺. The results demonstrate that functionalization of MOF by cation exchange without perturbing the crystallinity extends possibilities to achieve switchable materials.     

High‐Nuclear Organometallic Copper(I)–Alkynide Clusters: Thermochromic Near‐Infrared Luminescence and Solution Stability

Cu(CF₃COO)₂ reacts with tert‐butylacetylene (tBuC≡CH) in methanol in the presence of metallic copper powder to give two air‐stable clusters, [Cu^I₁₅(tBuC≡C)₁₀(CF₃COO)₅]?tBuC≡CH ( 1 ) and [Cu^I₁₆(tBuC≡C)₁₂(CF₃COO)₄(CH₃OH)₂] ( 2 ). The assembly process involves in situ comproportionation reaction between Cu²⁺ and Cu⁰ and the formation of two different clusters is controlled by reactants concentration. The clusters consist of Cu₁₅ and Cu₁₆ cores co‐stabilized by strong by σ‐ and π‐bonded tert‐butylethynide and CF₃COO^? (together with methanol molecule in 2 ). Their stabilities in solution were confirmed using electrospray ionization mass spectrometry in which the cluster core remains intact for 1 in chloroform and acetone, and for 2 in acetonitrile. Strong thermochromic luminescence in the near infrared (NIR) region was observed in the solid‐state. Of particular interest, the emission maximum of 1 is red‐shifted from 710 nm at 298 K to 793 nm at 93 K, along with a 17‐fold fluorescence enhancement. In contrast, 2 exhibits red shift from 298 to 123 K followed by blue shift from 123 to 93 K. The emission wavelength was correlated with the structural parameters using variable‐temperature X‐ray single‐crystal analyses. The rich cuprophilic interaction plays a significant role in the formation of ³LMCT (tBuC≡C→Cu_x) excited state mixed with cluster‐centered (³CC) characters, which can be considerably influenced by temperature, leading to thermochromic luminescence. The present work provides 1) a new synthetic protocol for the high‐nuclear Cu^I–alkynyl clusters; 2) a comprehensive insight into the mechanism of thermochromic luminescence; 3) unusual emissive materials with the characters of NIR and thermochromic luminescence simultaneously.     

In Situ Pyrolysis Tracking and Real-Time Phase Evolution: From a Binary Zinc Cluster to Supercapacitive Porous Carbon

The in situ tracking of the pyrolysis of a binary molecular cluster [Zn₇(μ₃-CH₃O)₆(L)₆][ZnLCl₂]₂ is presented with one brucite disk and two mononuclear fragments (L=mmimp: 2-methoxy-6-((methylimino)-methyl)phenolate) to porous carbon using TG-MS from 30 to 900 °C. Following up the spilled gas product during the decomposed reaction of zinc cluster along the temperature rising, and in conjunction with XRD, SEM, BET and other materials characterization, where three key steps were observed: 1) cleavage of the bulky external ligand; 2) reduction of ZnO and 3) volatilization of Zn. The real-time-dependent phase-sequential evolution of the remaining products and the processing of pore forming template transformation are proposed simultaneously. The porous carbon structure featuring a uniform nano-sized pore distribution synthesized at 900 °C with the highest surface area of 1644 m² g⁻¹ and pore volume of 0.926 cm³ g⁻¹ exhibits the best known capacitance of 662 F g⁻¹ at 0.5 A g⁻¹.     

Magnetic phase transitions in transition-metal complexes with triazole derivatives

Three divalent transition-metal (Co, Ni and Cu) complexes with the organic anion, 1,2,4-triazolato (tr), as a ligand molecule were prepared by means of hydrothermal syntheses and their magnetic properties were investigated by SQUID magnetometry. The Co(tr)₂ and Cu(tr)₂ complexes exhibit long range ordering below 8 and 30 K, respectively, while the Ni(tr)₂ complex does not show any magnetic phase transition down to 1.8 K. The magnetization isotherms of Co(tr)₂ and Cu(tr)₂ measured at 2.0 K show hysteresis loops with the coercive fields of 0.5 and 4.7 kOe, respectively. At temperatures higher than about 50 K, the temperature dependence of the magnetic susceptibility of Co(tr)₂, Ni(tr)₂ and Cu(tr)₂ follows the Curie-Weiss law with the Curie constants of 2.95, 0.945 and 0.420 emu K mol⁻¹ and the Weiss temperatures of −62, −74 and −97 K, respectively. These results suggest that the magnetically ordered phases observed in Co(tr)₂ and Cu(tr)₂ at low temperatures come from antiferromagnetic interactions resulting in canted arrangements of magnetic moments of the transition-metal cations. We discuss here the magnetic interactions in these transition-metal complexes by referring the results of the magnetization measurements.     

Co(II)5(OH)6(SO4)2(H2O)4: the first ferromagnet based on a layered cobalt-hydroxide pillared by inorganic...OSO3-Co(H2O)4-O3SO..

The synthetic mineral Co(II)5(OH)6(SO4)2(H2O)4 (1), obtained by hydrothermal reaction of CoSO4.7H2O and NaOH at 165 degrees C and consisting of brucite-like Co4(OH)6O2 layers pillared by OSO3-Co(H2O)4-O3SO, is a ferromagnet (T(Curie)= 12 K, Hc= 580 Oe).