Vacuum-Induced Guest ,'-Diethylformamide Binding in a Metastable Cd-Based Metal-Organic Framework.

A three-dimensional (3D) metal-organic framework (MOF) of [EtNH][Cd(BTB)(DEF)]·4.75DEF (; HBTB = benzene-1,3,5-tribenzoic acid and DEF = ,'-diethylformamide) sustained by symmetrical Z-shaped Cd secondary building units (SBUs) with an intrinsically metastable host framework has been prepared and characterized. Upon gentle vacuum (800 Pa) at 50 °C, some encapsulated DEF solvates are released, leading to pore-shape changes and Cd coordination geometry distortion.

Metal-organic frameworks of linear trinuclear cluster secondary building units: structures and applications.

Secondary building units (SBUs) in metal-organic frameworks (MOFs) are essential from both a structural and performance perspective. While a variety of SBUs, such as paddlewheel CuII2, triangular CrIII3, tetrahedral ZnII4, and octahedral ZrIV6 have been extensively studied, the linear trinuclear SBUs (herein denoted as M), though frequently encountered, are rarely discussed as a class. A literature survey reveals that M clusters are ubiquitous in discrete molecular entities as well as in MOFs.

A Heterometallic Three-Dimensional Metal-Organic Framework Bearing an Unprecedented One-Dimensional Branched-Chain Secondary Building Unit.

A heterometallic metal-organic framework (MOF) of [CdCa(BTB)(HCOO)(DEF)(HO)]∙DEF∙Sol (, HBTB = benzene-1,3,5-tribenzoic acid; DEF = ,'-diethylformamide; Sol. = undefined solvates within the pore) was prepared by solvothermal reaction of Cd(NO)·4HO, CaO and HBTB in a mixed solvent of DEF/HO/HNO. The compatibility of these two divalent cations from different blocks of the periodic table results in a solid-state structure consisting of an unusual combination of a discrete V-shaped heptanuclear cluster of [CdCa]Ca' and an infinite one-dimensional (1D) chain of [CdCaCa'] that are orthogonally linked via a corner-shared Ca ion (denoted as Ca'), giving rise to an unprecedented branched-chain secondary building unit (SBU).

An N,N'-diethylformamide solvent-induced conversion cascade within a metal-organic framework single crystal.

Crystals of a two-dimensional (2D) metal-organic framework (MOF) [Cd3(BTB)2(DEF)4]·2(DEF)0.5 (1; BTB = benzene-1,3,5-tribenzolate; DEF = N,N'-diethylformamide) immersed in a solution of trans-1,2-bis(4-pyridyl)ethylene (BPEE) yields an interpenetrated three-dimensional (3D) MOF of [Cd3(BTB)2(BPEE)(H2O)2]·(BPEE)·xSol (2). Crystals of MOF 2, in turn, undergo a cascade conversion when immersed in DEF, yielding [Cd3(BTB)2(BPEE)1.

Unconventional Pyridyl Ligand Inclusion within a Flexible Metal-Organic Framework Bearing an N,N'-Diethylformamide (DEF)-Solvated Cd Cluster Secondary Building Unit.

A cationic three-dimensional (3D) metal-organic framework (MOF) sustained by an N,N'-diethylformamide (DEF)-solvated zigzag-shaped Cd cluster secondary building unit (SBU), [Et NH ] [Cd (BTB) (DEF) ] ⋅ 4.75DEF (1 a, H BTB=benzene-1,3,5-tribenzoic acid) shows flexible framework behavior and undergoes solvate exchange with CHCl to yield [Et NH ] [Cd (BTB) (DEF) ] ⋅ xCHCl (1 b) accompanied by changes to pore sizes and shapes. Unexpectedly, the DEF solvates coordinated to the central Cd could not be replaced by strongly donor pyridyl and dipyridyl ligands.

Intramolecular Nitrene Insertion into Saturated C-H-Bond-Mediated C-N Bond Cleavage of a Coordinated NHC Ligand.

Ruthenium(II) complexes bearing a tridentate bis(N-heterocyclic carbene) ligand reacted with iminoiodanes (PhI=NR) resulting in the formation of isolable ruthenium(III)-amido intermediates, which underwent cleavage of a C-N bond of the tridentate ligand and formation of an N-substituted imine group. The Ru -amido intermediates have been characterized by H NMR, UV/Vis, ESI-MS, and X-ray crystallography. DFT calculations were performed to provide insight into the reaction mechanism.

Smoothing the single-crystal to single-crystal conversions of a two-dimensional metal-organic framework via the hetero-metal doping of the linear trimetallic secondary building unit.

The two-dimensional (2D) metal-organic framework (MOF) [Cd2.25Co0.75(BTB)2(DEF)4]·2(DEF)0.

Evaluating the component contribution to nonlinear optical performances using stable [NiO] cuboidal clusters as models.

Five stable clusters sharing the cuboidal [Ni4O4] skeleton are subjected to third-order nonlinear optical (NLO) property measurements. Preliminary results suggest that the NLO property is largely defined by the cluster core skeleton and the directly coordinated atoms, with limited contribution from the heavy atoms peripherally attached to the aromatic ligands.

Co₂ and Co₃ Mixed Cluster Secondary Building Unit Approach toward a Three-Dimensional Metal-Organic Framework with Permanent Porosity.

Large and permanent porosity is the primary concern when designing metal-organic frameworks (MOFs) for specific applications, such as catalysis and drug delivery. In this article, we report a MOF Co(BTB)₆(NO₃)₄(DEF)₂(H₂O) (, H₃BTB = 1,3,5-tris(4-carboxyphenyl)benzene; DEF = ,-diethylformamide) via a mixed cluster secondary building unit (SBU) approach. MOF is sustained by a rare combination of a linear trinuclear Co₃ and two types of dinuclear Co₂ SBUs in a 1:2:2 ratio.

Deciphering the Structural Relationships of Five Cd-Based Metal-Organic Frameworks.

The one-pot reaction of Cd(NO)·4HO and 5-(6-(hydroxymethyl)pyridin-3-yl)isophthalic acid (HL) in DMF/HO (DMF = N,N-dimethylformamide) produced a two-dimensional (2D) metal-organic framework (MOF) of [Cd(L)(HO)] (A) bearing aqua-bridged Cd centers, accompanied by two three-dimensional (3D) MOFs [Cd(L)(DMF)] (B) and [Cd(L)] (C). Removing the bridging aqua molecules of A by heating led to the formation of an additional 3D MOF of [Cd(L)] (D) in a single-crystal to single-crystal (SCSC) manner. The search for the preceding compound that could convert to A resulted in the isolation of a 2D MOF [Cd(L)(DMF)] (E) that readily converted to A in water, but with the loss of single crystallinity.