Entanglement of Square Nets in Covalent Organic Frameworks

Two entangled 2D square COFs have been synthesized from 4,4',4'',4'''-(9,9'-spirobi[fluorene]-2,2',7,7'-tetrayl)-tetrabenzaldehhyde (SFTB) and p-phenylenediamine (PPA) and benzidine (BZD) to form COF-38, [(SFTB)(PPA)2]imine and its isoreticular form COF-39, [(SFTB)(BZD)2]imine. We also report the single crystal electron diffraction structure of COF-39 and find that it is composed of mutually entangled 2D square nets (sql). These COFs represent the first examples of entangled 2D COF structures, which as we illustrate were made possible by our strategy of using the distorted tetrahedral SFTB building unit. SFTB overcomes the propencity of 2D COFs to stack through π-π stacking and allows for entanglements to form. This work adds significantly to the design principles of COFs.

A simple pressure-assisted method for MicroED specimen preparation

Micro-crystal electron diffraction (MicroED) has shown great potential for structure determination of macromolecular crystals too small for X-ray diffraction. However, specimen preparation remains a major bottleneck. Here, we report a simple method for preparing MicroED specimens, named Preassis, in which excess liquid is removed through an EM grid with the assistance of pressure. We show the ice thicknesses can be controlled by tuning the pressure in combination with EM grids with appropriate carbon hole sizes. Importantly, Preassis can handle a wide range of protein crystals grown in various buffer conditions including those with high viscosity, as well as samples with low crystal concentrations. Preassis is a simple and universal method for MicroED specimen preparation, and will significantly broaden the applications of MicroED.

A simple pressure-assisted method for MicroED specimen preparation

Micro-crystal electron diffraction (MicroED) has shown great potential for structure determination of macromolecular crystals too small for X-ray diffraction. However, specimen preparation remains a major bottleneck. Here, we report a simple method for preparing MicroED specimens, named Preassis, in which excess liquid is removed through an EM grid with the assistance of pressure. We show the ice thicknesses can be controlled by tuning the pressure in combination with EM grids with appropriate hole sizes. Importantly, Preassis can handle a wide range of protein crystals grown in various buffer conditions including those with high viscosity, as well as samples with low crystal contents. Preassis is a simple and universal method for MicroED specimen preparation, and will significantly broaden the applications of MicroED.

Experimental Charge Density Analysis and Electrostatic Properties of Crystalline 1,3-Bis(Dimethylamino)Squaraine and Its Dihydrate from Low Temperature (T = 18 and 20 K) XRD Data

Multipolar refinements of structural models fitting extensive sets of X-ray diffraction (XRD) data from single crystals of 1,3-bis(dimethylamino)squaraine [SQ, C8H12N2O2] and its dihydrate [SQDH, C8H12N2O2·2H2O], collected at very low T (18 ± 1 K for SQ, 20 ± 1 K for SQDH), led to an accurate description of their crystal electron density distributions. Atomic volumes and charges have been estimated from the experimental charge densities using the Quantum Theory of Atoms in Molecules (QTAIM) formalism. Our analysis confirms the common representation (in the literature and textbooks) of the squaraine central, four-membered squarylium ring as carrying two positive charges, a representation that has been recently questioned by some theoretical calculations: the integrated total charge on the C4 fragment is estimated as ca. +2.4e in SQ and +2.2e in SQDH. The topology of the experimental electron density for the SQ squaraine molecule is modified in the dihydrated crystal by interactions between the methyl groups and the H2O molecules in the crystal. Maps of the molecular electrostatic potential in the main molecular planes in both crystals clearly reveal the quadrupolar charge distribution of the squaraine molecules. Molecular quadrupole tensors, as calculated with the PAMoC package using both Stewart and QTAIM distributed multipole analysis (DMA), are the same within experimental error.

Single Crystal of a One-dimensional Covalent Organic Framework

Although polymers have been studied for well over a century, there are few examples of covalently linked polymer crystals synthesized directly from solution. One-dimensional (1D) covalent polymers that are packed into a framework structure can be viewed as a 1D covalent organic framework (COF), but making single crystal of this has been elusive. Herein, by combining labile metal coordination and dynamic covalent chemistry, we discovered a strategy to synthesize single-crystal metallo-COF under solvothermal conditions. The single-crystal structure was rigorously solved using single-crystal electron diffraction (SCED) technique. The non-centrosymmetric metallo-COF allows second harmonic generation (SHG). Due to the presence of syntactic pendant amine groups along the polymer chains, the metallopolymer crystal can be further cross-linked into a crystalline woven network.

Single Crystal of a One-dimensional Covalent Organic Framework

Although polymers have been studied for well over a century, there are few examples of covalently linked polymer crystals synthesized directly from solution. One-dimensional (1D) covalent polymers that are packed into a framework structure can be viewed as a 1D covalent organic framework (COF), but making single crystal of this has been elusive. Herein, by combining labile metal coordination and dynamic covalent chemistry, we discovered a strategy to synthesize single-crystal metallo-COF under solvothermal conditions. The single-crystal structure was rigorously solved using single-crystal electron diffraction (SCED) technique. The non-centrosymmetric metallo-COF allows second harmonic generation (SHG). Due to the presence of syntactic pendant amine groups along the polymer chains, the metallopolymer crystal can be further cross-linked into a crystalline woven network.