Toward step-by-step nuclear growth of surface two-dimensional porphyrin nanonetworks

Abstract

We report the development of a solution-based step-by-step technique, which utilizes the coordination bond between metalloporphyrin molecular units and metal linkages and results in the nuclear growth of nano-networks on solid substrates. The growth of the surface structures is strongly influenced by the choice of substrate materials and solvents: the molecule-substrate interaction and the solubility of the molecular units are important parameters in tuning the size and growth of the domains.

A Porphyrin Spin Qubit and Its 2D Framework Nanosheets

“…Nanosheet domains similar to those fabricated by the Langmuir–Schaefer protocol are visible, with lateral sizes within the expected 50–100 nm range and heights of ≈3.3 nm. Very few higher domains with heights up to 15 nm are also observed, but likely due to an unoptimized washing procedure . When omitting the addition of the [Cu(H 4 TCPP)] solution no domain at all are formed (Figure S27, Supporting Information), corroborating the domain formation emerges from the in situ coordination of the metalloporphyrin units and the Zn(II) ions.…”

“…As mentioned here and demonstrated previously, the MOF crystalline nanosheets are built at the air/liquid interface by self‐assembly upon reaction of the [Cu(TCPP)] metalloporphyrin building unit and the Zn(II) ions in the aqueous subphase. Interestingly, these nanoassemblies also form when following procedures of alternate immersions of a substrate in adequate solutions, suggesting the 2D nanosheet formation is inherent to this MOF coordinative reaction. We therefore devised a protocol aimed at local on‐surface 2D MOF formation, taking advantage of the fact the nanosheet formation is expected to proceed instantaneously .…”

Construction of a two-dimensional metal–organic framework with perpendicular magnetic anisotropy composed of single-molecule magnets

“…The PXRD pattern of 1Pd exhibits a strong diffraction peak at 9.55°, which corresponds to a lattice plane distance ( d ) of 9.25 Å. Based on this d value and the assumption that Pd 2+ adopts a square planar coordination geometry, 31,37 the structure of 1Pd was expected, as shown in Fig. 3d.…”

“…In particular, the Py unit can form stable coordination bonds with the Pd 2+ ion. 31 Therefore, in the presence of Pd 2+ , 1 forms an ordered and preferentially oriented nanosheet (Fig. 1c).…”

Two-Dimensional Porphyrinic Metal–Organic Framework Composites as a Photocatalytic Platform for Chemoselective Hydrogenation

“…As an emerging class of porous materials, 2D metal–organic framework (MOF) nanosheets have attracted considerable attention not only due to the general advantages of MOFs but also due to the unique properties of ultrathin thickness, large surface area, and highly accessible active sites without diffusion constraints. − Being one of the most frequently found species in nature, porphyrins have been used as linkers, giving rise to 2D porphyrinic metal–organic frameworks (2D PMOFs), − which could display photocatalytic performances based on the following advantages: (i) Porphyrin ligands are capable of absorbing visible light. (ii) Various elements ranging from transition metals to main group elements have been incorporated into the porphyrin rings, enlarging the catalytic reaction scope. − (iii) Functional species, which can finely regulate the layer spacing and electron transfer pathway without affecting the structure of the network, can be anchored in the nodes or linkers of MOFs. ,, …”