Crystalline nanosheets of three-dimensional supramolecular frameworks with uniform thickness and high stability.

Fabricating three dimensional (3D) supramolecular frameworks (SMFs) into stable crystalline nanosheets remains a great challenge due to the homogeneous and weak inter-building block interactions along 3D directions. Herein, crystalline nanosheets of a 3D SMF with a uniform thickness of 4.8 ± 0.

Hydrophobic Trinuclear Copper Cluster-Containing Organic Framework for Synergetic Electrocatalytic Synthesis of Amino Acids.

Electrocatalytic synthesis of amino acids provides a promising green and efficient pathway to manufacture the basic substances of life. Herein, reaction of 2,5-perfluroalkyl-terepthalohydrazide and tris(4-µ -O-carboxaldehyde-pyrazolato-N, N')-tricopper affords a crystalline trinuclear copper cluster-containing organic framework, named F-Cu -OF. Incorporation of abundant hydrophobic perfluroalkyl groups inside the channels of F-Cu -OF is revealed to successfully suppress the hydrogen evolution reaction via preventing H cation with large polarity from the framework of F-Cu -OF and in turn increasing the adsorption of other substrates with relatively small polarity like NO and keto acids on the active sites.

Post-Nickelation of a Crystalline Trinuclear Copper Organic Framework for Synergistic Photocatalytic Carbon Dioxide Conversion.

Rational regulation of electronic structures and functionalities of framework materials still remains challenging. Herein, reaction of 4,4',4''-nitrilo-tribenzhydrazide with tris(μ -4-carboxaldehyde-pyrazolato-N,N')-tricopper (Cu Py ) generates the crystalline copper organic framework USTB-11(Cu). Post-modification with divalent nickel ions affords the heterometallic framework USTB-11(Cu,Ni).

Two-Dimensional Porphyrin-Based Covalent Organic Framework with Enlarged Inter-layer Spacing for Tunable Photocatalytic CO Reduction.

Two-dimensional (2D) porphyrin-based covalent organic frameworks (COFs) are one of the most promising candidates for photocatalytic carbon dioxide reduction reaction (CORR), which however still suffer from the hindered mass transfer during the catalysis procedure associated with the close packing of 2D COF layers due to the strong axial π-π stacking. Herein, condensation between the porphyrinic aldehydes -MPor-CHO (M = H, Co, and Ni) and 3,8-diamino-6-phenyl-phenanthridine (DPP) affords new porphyrin-based 2D COF architecture MPor-DPP-COFs (M = H, Co, and Ni). The bulky phenyl substituent at the phenanthridine periphery of the linking unit reduces the axial π-π stacking, providing an enlarged inter-layer spacing of 6.