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 (~ C2h 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:

4c_vs_2_3_c_Image

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):

nbo_vs_fof

Likewise tetratopic linkers with two pairs of connection points twisted by ~ 90° (~ D2d 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:

DUT-11_Linker_4c_vs_3c

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

pts_vs_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:

pts_derived_nets

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

What’s your opinion about that issue?

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