Basic and derived nets – poster available

A new poster is made available showing an overview of all basic and derived nets of the RCSR.

Feel free to download and share it!

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MOF nets overview

On a subpage of this blog a table-like overview of MOFs and their respective underlying nets are gathered – will be expanded from time to time!

https://crystalsymmetry.wordpress.com/nets/mof-nets/

Basic and derived nets

There is an ongoing discussion on the question how certain metal-organic frameworks (MOFs) should be deconstructed in the most appropriate way in order to obtain their underlying nets.

The majority of cases of uncertainties are dealing with different ways of deconstructing certain classes of polytopic linkers. For example, an elongated planar tetracarboxylate linker (~ C_2h symmetry) can be regarded as one 4-coordinated vertex (square or rectangular local geometry) or as two 3-c vertices joined by an extra edge (two triangles in the same plane), see the following figure:

The most prominent example is MOF-505 [DOI: 10.1002/anie.200462787] (identical with NOTT-100 [DOI: 10.1002/anie.200601991]) based on the 4-c square-planar Cu paddle-wheel motif as inorganic secondary building units (SBU), and the question arises if the underlying net is nbo (cubic, 4-c uninodal) or fof (trigonal, (3,4)-c binodal):

Likewise tetratopic linkers with two pairs of connection points twisted by ~ 90° (~ D_2d symmetry) can be regarded as one 4-c vertex ([distorted] tetrahedral local geometry) or as two 3-c vertices (two triangles joined by an extra edge and being perpendicular oriented to each other), as shown in the following figure:

One example is DUT-11 (DOI: 10.1002/ejic.201000415). Here, the underlying net can be described either as pts or sur:

There are arguments for and against a far-reaching compartimentalization of the linker, i.e. to explicitly take into account the additional branching points within the linker or not. It has been argued, for example, that tetratopic linkers should always regarded as a single 4-c node, because this would reflect its chemical nature more appropriately. However, there are at least two arguments against the single 4-c consideration: (i) the local geometry and the shape of the linker is represented very badly; (ii) a considerable amount of topological information would be lost, if two 3-c vertices are fused into one single 4-c vertex; if we take the example of the (4,4)-c net pts (“tetrahedra plus squares”) there are no less than six different topologies that can be derived by splitting either the 4-c tetrahedron into two 3-c vertices or the 4-c square into two 3-c vertices and there are no clear reasons why all these should be indiscriminately classified as their parent net pts, see the following figure:

(All nets are shown in their augmented versions – see here.)

What’s your opinion about that issue?

Augmentation of nets

An augmented net, which is indicated by an appendix -a to the three letter code of the basic net, is obtained from its underlying basic net by replacing all vertices with their respective coordination figure, i.e. polyhedron or polygon. For instance, all the vertices of the bcu net are replaced with cubes, and the (two different kinds of) 4-coordinated vertices of the pts net with squares and tetrahedra, respectively (see Figure below).

The first obvious advantage of such representations is that it is much easier to identify and to perceive the actual coordination environment of the vertices; not only the coordination number and type, but also their relative orientation to each other, so the local geometry of the vertices is explicitly included and visualized. In this sense it is also helpful in terms of a more intuitive or visual way of classification of nets, for instance, if we investigate all the possible nets that are assembled by a combination of certain node-types, say, tetrahedra and triangles, or trigonal prisms with squares and so on. However, augmentation is beneficial in particular in order to elucidate relationships between nets that are similar to each other: Note that the vertices of the augmented version of a given net have different coordination numbers, coordination sequences and vertex symbols; and these specifications – the topology – may be identical with another basic net that has been derived by the deconstruction of the chemical compound leading to this specific net description, for instance bcu-a is identical with the net of polycubane (pcb).